INTERACTIONS OF GROUP 13 LEWIS ACIDS WITH
HEXACHLOROCYCLOTRIPHOSPHAZENE
A Thesis
Presented to
The Graduate Faculty of the University of Akron
In Partial Fulfillment
of the Requirements for the Degree
Master of Science
Zin-Min Tun
December, 2008
INTERACTIONS OF GROUP 13 LEWIS ACIDS WITH
HEXACHLOROCYCLOTRIPHOSPHAZENE
Zin-Min Tun
Thesis
Approved:
Accepted:
Advisor
Dr. Claire A. Tessier
Dean of the College
Dr. Ronald F. Levant
Co-Advisor
Dr. Wiley J. Youngs
Dean of the Graduate School
Dr. George R. Newkome
Department Chair
Dr. Kim C. Calvo
Date
ii
DEDICATION
To my beloved husband
iii
ACKNOWLEDGEMENTS
First and foremost, I would like to thank my advisor, Dr. Claire A. Tessier.
She has been my inspiration not only as a scientist but also as an individual. I
was not one of those people who always knew what they wanted out of life. But I
was lucky enough to have taken a class from Dr. Tessier as an undergraduate
student. She inspired me so much that I decided to do undergraduate research
the following semester. While being a research assistant in her group, I came to
the realization that I wanted to be a researcher and decided to pursue a graduate
degree. To me, she is an advisor, a mentor, a friend, a parent and a role-model,
and I have always been able to draw strength from her faith in my ability in times
of self-doubt.
I would also like to thank my co-advisor, Dr. Wiley J. Youngs for his many
helpful ideas and suggestions for my research. I also received a lot of help and
support throughout my graduate career from several group members, past and
present. I have deep appreciation especially for Dr. Matthew J. Panzner and Dr.
Monica Soler. They have always shown interest in my research and have been
constant sources of knowledge and support for me. I have also found help in Dr.
Khadijah Hindi, Dr. Doug Medvetz, Dr. Paul Custer and Dr. Tatiana Eliseeva. I
would like to thank the former group member, Dr. Amy J. Heston who had started
iv
the phosphazene research in our group. I would also like to thank Brian Wright,
Nikki Robishaw, and Supat Moolsin for being good friends since the
undergraduate days. I am thankful to Linlin Li for all her help with the NMR and
for being such a good study-partner.
I am grateful to have met my host-parents, Jim and Janelle Collier. They
have been kindness itself to me over the years. Their love and faith in me had
seen me through many difficult times in life, including the time when I had iritis
and feared that I might lose my vision. I have met many other people throughout
the life who have done many random acts of kindness for me and I hope to be
able to pay back their kindness one day by paying it forward.
I am also thankful to my parents who believed in me and let me come to
the United States for my education. I understand that letting me go is a very
difficult and selfless act from their part. I would also like to thank my sister, Dr.
Swe Zin Tun. She has always been there for me and has shared my pain as well
as my happiness as her own. She is not only the best sister but also the best
friend I could ever ask for in life.
Last but not least, I would like to thank my husband, Brian Darby. In
finding him, I have found myself. His love, understanding and encouragement
have given me the strength and the focus to go after what I really want to be in
life regardless of what other people say. While I was writing this thesis, he said,
“Tell me what you need me to do. I got your back.” I thank him from the bottom of
my heart for all his help and patience. I am very blessed to have him as my life
partner and I can just hope to be to him what he is to me.
v
TABLE OF CONTENTS
Page
LIST OF FIGURES .............................................................................................viii
LIST OF SCHEMES.............................................................................................. x
CHAPTER
I. INTRODUCTION ............................................................................................. 1
1.1. Introduction ................................................................................................ 1
1.2. Synthesis of Phosphazene Polymer .......................................................... 1
1.3. Interactions of [PCl2N]3 with Lewis acids.................................................... 7
II. EXPERIMENTAL ............................................................................................ 9
2.1. General Experimental Methods ................................................................. 9
2.2. Materials Used ........................................................................................... 9
2.3. Spectroscopy ........................................................................................... 10
2.4. Purification of [PCl2N]3 ............................................................................. 10
2.5. Interaction of [PCl2N]3 with AlCl3 .............................................................. 11
2.5.1. Purification of AlCl3 ............................................................................. 11
2.5.2. Synthesis of [PCl2N]3.AlCl3 .................................................................. 11
2.6. Interaction of [PCl2N]3 with AlBr3 .............................................................. 12
2.6.1. Purification of AlBr3 ............................................................................. 12
2.6.2. Synthesis of [PCl2N]3.AlBr3.................................................................. 12
vi
2.7. Interaction of [PCl2N]3 with GaCl3 ............................................................ 13
2.7.1. Purification of GaCl3 ............................................................................ 13
2.7.2. Synthesis of [PCl2N]3.GaCl3 ................................................................ 13
2.8. Interaction of [PCl2N]3 with BCl3 ............................................................... 14
2.9. Interaction of [PCl2N]3 with BBr3............................................................... 14
2.10. Interaction of [PCl2N]3 with InCl3 ............................................................ 15
III. RESULTS AND DISCUSSION..................................................................... 16
3.1. Interactions of [PCl2N]3 with Lewis Acids ................................................. 16
3.2. X-ray Crystallography .............................................................................. 17
3.2.1. [PCl2N]3.AlCl3 adduct........................................................................... 17
3.2.2. [PCl2N]3.AlBr3 adduct .......................................................................... 19
3.2.3. [PCl2N]3.GaCl3 adduct ......................................................................... 21
3.3. NMR Studies............................................................................................ 24
3.3.1. VT NMR of [PCl2N]3.AlCl3 adduct ........................................................ 26
3.3.2. VT NMR of [PCl2N]3.AlBr3 adduct........................................................ 33
3.3.3. VT NMR of [PCl2N]3.GaCl3 adduct ...................................................... 39
3.4. Comparison of [PCl2N]3.AlCl3, [PCl2N]3.AlBr3 and
[PCl2N]3.GaCl3 addcuts ............................................................................ 50
IV. CONCLUSION............................................................................................. 52
REFERENCES ................................................................................................... 54
APPENDIX.......................................................................................................... 56
vii
LIST OF FIGURES
Figure
Page
1.1.
The Phosphazene Polymer Backbone ....................................................... 1
1.2.
Proposed Structures of the Product of Interactions between
Lewis Acids and [PCl2N]3 ........................................................................... 7
3.1.
Thermal Ellipsoid Plot of [PCl2N]3.AlCl3 .................................................... 18
3.2.
Thermal Ellipsoid Plot of [PCl2N]3.AlBr3.................................................... 20
3.3.
Thermal Ellipsoid Plot of [PCl2N]3.GaCl3 .................................................. 22
3.4.
Thermal Ellipsoid Plot of the Asymmetric Unit of
[PCl2N]3.AlCl3 .......................................................................................... 23
3.5.
31
3.6.
31
3.7.
31
3.8.
31
3.9.
31
3.10.
31
3.11.
1
3.12.
31
3.13.
31
P NMR Spectra of [PCl2N]3.AlCl3, [PCl2N]3.AlBr3 and
[PCl2N]3.GaCl3 in CDCl3 at 25 °C ............................................................. 25
P NMR Spectra of [PCl2N]3.AlCl3 in CDCl3 at 55 °C .............................. 27
P NMR Spectra of [PCl2N]3.AlCl3 in CDCl3 at 40 °C .............................. 28
P NMR Spectra of [PCl2N]3.AlCl3 in CDCl3 at 30 °C .............................. 29
P NMR Spectra of [PCl2N]3.AlCl3 in CDCl3 at 0 °C ................................ 30
P NMR Spectra of [PCl2N]3.AlCl3 in CDCl3 at -20 °C ............................. 31
H NMR Spectra of [PCl2N]3.AlCl3 in CDCl3
at 40 °C, 30 °C, 0 °C, and -20 °C............................................................ 32
P NMR Spectra of [PCl2N]3.AlBr3 in CDCl3 at 25 °C .............................. 34
P NMR Spectra of [PCl2N]3.AlBr3 in CDCl3 at 0 °C ................................ 35
viii
3.14.
31
P NMR Spectra of [PCl2N]3.AlBr3 in CDCl3 at -20 °C............................ 36
3.15.
31
3.16.
1
3.17.
31
3.18.
31
3.19.
31
3.20.
31
3.21.
31
3.22.
31
3.23.
31
3.24.
31
3.25.
31
3.26.
1
P NMR Spectra of [PCl2N]3.AlBr3 in CDCl3 at -40 °C............................. 37
H NMR Spectra of [PCl2N]3.AlBr3 in CDCl3
at 25 °C, 0 °C, -20 °C and -40 °C............................................................ 38
P NMR Spectra of [PCl2N]3.GaCl3 in CDCl3 at 35 °C............................. 40
P NMR Spectra of [PCl2N]3.GaCl3 in CDCl3 at 30 °C............................. 41
P NMR Spectra of [PCl2N]3.GaCl3 in CDCl3 at 25 °C............................. 42
P NMR Spectra of [PCl2N]3.GaCl3 in CDCl3 at 15 °C............................. 43
P NMR Spectra of [PCl2N]3.GaCl3 in CDCl3 at 0 °C............................... 44
P NMR Spectra of [PCl2N]3.GaCl3 in CDCl3 at -20 °C............................ 45
P NMR Spectra of [PCl2N]3.GaCl3 in CDCl3 at -40 °C............................ 46
P NMR Spectra of [PCl2N]3.GaCl3 in CDCl3 at -50 °C............................ 47
P NMR Spectra of [PCl2N]3.GaCl3 in CDCl3 at -55 °C............................ 48
H NMR Spectra of [PCl2N]3.GaCl3 in CDCl3 at -55 °C,-50 °C,
-40 °C, -20 °C, 0 °C, 15 °C, 25 °C, and 30 °C......................................... 49
ix
LIST OF SCHEMES
Scheme
Page
1. Functionalization of Chlorophosphazenes ................................................. 2
2. Synthesis Routes of Chlorophosphazene Polymer .................................... 3
3. Mechanism of ROP of [PCl2N]3 Proposed by Emsley ................................ 5
4. Mechanism of ROP of [PCl2N]3 Proposed by Allcock................................. 6
x
CHAPTER I
INTRODUCTION
1.1.
Introduction
Phosphazene polymers have inorganic backbones made of alternating
phosphorous and nitrogen atoms. Each phosphorous can have two substituents
that are either organic or inorganic (Figure 1.1).
R
R'
R
P
P
N
N
N
N
P
R
R'
R'
P
R
R'
Figure 1.1. The Phosphazene Polymer Backbone
1.2. Synthesis of Phosphazene Polymer
Most functional polyphosphazenes are made by replacing chlorides on the
highly reactive chlorophosphazenes with (OR) or (NR2) substituents in high yield
reactions (Scheme 1).1 By varying the substituents, polyphosphazenes can be
tailor-made to meet a variety of functional needs. In general, when the
substituents are OR groups, the resulting phosphazene polymer is very stable
and flexible and it can be used as elastomers, foams, fire-proofing, batteries,
1
contact lenses, and coatings.2 With NR2 substituents, phosphazene polymers
become water degradable and can be used as coating for time released drugs.2
OR
P N
OR
Cl
OR
n
P N
Cl
NR2
n
NR2
P N
NR2
n
Scheme 1. Functionalization of Chlorophosphazenes.1
However, synthesis of the reactive chlorophosphazenes either requires
expensive starting materials or it is hard to reproduce and has low yield.
Therefore, fundamental chlorophosphazene chemistry needs to be understood in
order to tap into the wide range of possible applications offered by
polyphosphazenes.
There are several routes to synthesize chlorophosphazene polymers as
shown in Scheme 2. Of the routes listed, the ring opening polymerization (ROP)
of hexachlorocyclotriphosphazene, [PCl2N]3 at ~ 250 °C is the traditional route.
This route has irreproducibility issues but it uses cheap starting materials.
Because other routes require expensive starting materials, our goal was to study
the fundamental chemistry of [PCl2N]3 in order to understand the causes of the
low-yield and irreproducibility issues in its ROP.
2
3
Scheme 2. Synthesis Routes of Chlorophosphazene Polymers
There are two different mechanisms of the ROP of [PCl2N]3 that were
proposed by Emsley and Allcock.3,4 Scheme 3 and 4 show these two
mechanisms. In Emsley’s mechanism,3 which is depicted in Scheme 3, the
nitrogen on [PCl2N]3 gets protonated in the first step. The protonation weakens
and breaks the bond between the nitrogen and a neighboring phosphorous,
which opens the ring, leaving a lone pair on nitrogen and creating a
phosphazenium cation. The lone pair on nitrogen attacks a phosphorous on
another [PCl2N]3 and polymerization is started.
The mechanism proposed by Allcock4 is the more commonly accepted
mechanism and it is shown in Scheme 4. One chloride on [PCl2N]3 is removed in
the first step, forming a phosphazenium cation. A lone pair of nitrogen on another
[PCl2N]3 attacks the cation, and as a result, the second [PCl2N]3 is ring-opened,
forming another phosphazenium cation and initiating the ROP process.
According to this mechanism, adding a Lewis acid, which could act as a halide
abstractor, in the ROP should promote the first step involving the removal of a
chloride. This hypothesis is supported by one of the synthesis routes of [PCl2N]n
listed in Scheme 2, where adding BCl3 lowers the ROP temperature to 210 °C
compared to uncatalyzed ROP temperature at ~ 250 °C. Therefore, it is
important to understand the interaction of [PCl2N]3 with Lewis acids.
4
5
Scheme 3. Mechanism of ROP of [PCl2N]3 Proposed by Emsley3
6
Scheme 4. Mechanism of ROP of [PCl2N]3 Proposed by Allcock4
1.3. Interactions of [PCl2N]3 with Lewis acids
The interactions of [PCl2N]3 with Lewis acids have been studied since
1940’s. Although interactions with several Lewis acids had been reported prior to
our group’s work,4-8 the product of interactions were poorly characterized in some
of the reports. The structures of the products of these interactions were proposed
to be either 1 or 2 in Figure 1.2 or their variants.8,9 The actual structure of the
adducts was still a subject of debate when our group started our research. For
the Lewis acids studied here in, BCl3, AlCl3, AlBr3 and GaCl3, very different
products were proposed. For BCl3, an adduct of structure 1 was proposed as an
intermediate in the BCl3 initiated ROP of [PCl2N]3 at 210 °C.7, 8 AlCl3 was
reported to react with [PCl2N]3 to give a bis cation related to 2.10 GaCl3 was
reported not to react with [PCl2N]3.11
LA = Lewis acid
LA
Cl
Cl
LA(Cl)
N
Cl
P
P
N
N
Cl
Cl
Cl
N
P
N
P
Cl
P
Cl
N
P
Cl
Cl
1
Cl
2
Figure 1.2. Proposed Structures of the Product of Interactions between Lewis
Acids and [PCl2N]3.
7
Previous work in our group had focused on the reactions between
[PCl215N]3 and Lewis acids.12, 13 The purpose of using 15N labeled starting
materials was to fully utilize NMR techniques in characterizing the products by
introducing the NMR active 15N into the compounds. However, our group’s
findings showed that there was an exchange process occurring in the Lewis acid
adducts of [PCl215N]3 in solution. Due to the rapid exchange, the NMR
resonances coalesced and it was difficult to assign the structure of the product in
the solution state based on the NMR studies. We concluded that, in order to
understand the fluxional nature of the products, it would be best to study the
interactions of Lewis acids with non-labeled [PCl2N]3.
Accordingly, the focus of this work was on the interactions of non-labeled
[PCl2N]3 with Group 13 Lewis acids. Group 13 adducts of [PCl2N]3 previously
reported were [PCl2N]3.AlBr3 and [PCl2N]3.(AlCl3)2.5, 10 GaCl3 was reported not to
form adducts with [PCl2N]3.11 Although BCl3 had been used as a catalyst in the
ROP process,7, 8 its adducts with [PCl2N]3 had not been isolated. The goal of this
work was to investigate the interactions of [PCl2N]3 with Group 13 Lewis acids
AlCl3, AlBr3, GaCl3, BCl3, BBr3, and InCl3 and to study the products, especially
their fluxional natures, by using modern characterization methods.
8
CHAPTER II
EXPERIMENTAL SECTION
2.1. General Experimental Methods
All manipulations were carried out under vacuum or under dry and
oxygen-free argon atmosphere. Standard anaerobic techniques such as Schlenk,
vacuum line and glove-box techniques were applied.14-16 The vacuum line had
the ultimate capacity of 2x10-4 torr. All glassware was dried in the oven overnight.
The hot glassware was assembled hot and evacuated immediately, or directly
placed in the port of the glove-box, evacuated and assembled in the box.
2.2. Materials Used
([PCl2N]3) (Aldrich, 99.99%) was further purified by sublimation. AlCl3,
AlBr3, and GaCl3 (Alfa Aesar, ampoule, 99.999%) were sublimed before use.
BCl3 was purchased from Aldrich as a 1M solution in heptane and was used
without further purification. BBr3 (Aldrich) was degassed before use. InCl3
(99.999%) was used as received in an ampoule from Aldrich. The solvents
hexane and chloroform were purified using a PureSolvTM system. Deuterated
chloroform was purchased from Cambridge Isotopes, distilled three times from
regenerated 4 Å molecular sieves and stored under argon.
9
2.3. Spectroscopy
Proton and 31P NMR spectra were taken on Varian INOVA 400 MHz or
Varian 500 MHz spectrometers. Proton NMR spectra were referenced to the
residual proton resonance in the deuterated solvent, and 31P NMR spectra were
externally referenced to phosphoric acid (0 ppm). In order to exclude moisture
from the samples, NMR tubes were flame sealed under vacuum. Variable
Temperature NMR (VT NMR) studies were performed by Dr. Deepa Savant and
the author. For X-ray crystallographic analysis, crystals were placed on a slide
and covered with paratone oil. The slide was transported from the glove-box to
the diffractometer in a desiccator that was covered with aluminum foil. Crystals
were immediately mounted in the dark. Crystallographic data were acquired on a
Bruker SMART Apex CCD diffractometer and structure solution and refinement
were done using the Bruker SHELXTL package. Crystal structure analyses were
done by Dr. Matthew J. Panzner, Dr. Doug Medvetz, and Brian Wright.
2.4. Purification of [PCl2N]3
[PCl2N]3 (5 g) was placed in a sublimator. The sublimation was carried out
on the high vacuum line overnight at ~60 °C. The sublimate (4.7 g) was collected
in the glove box and stored in an amber vial in the glove box until use.
10
2.5. Interaction of [PCl2N]3 with AlCl3
In order to avoid protonated impurities, high vacuum line and glove box
techniques were used instead of the Schlenk line. Because the [PCl2N]3.AlCl3
adduct was light sensitive, exposure to light was minimized throughout all
phases of the work.
2.5.1. Purification of AlCl3
The sealed glass ampoule containing AlCl3 (5 g) was scored open in the
glove box. AlCl3 was put in a sublimator and a thin layer of glass wool that had
been pre-dried in an oven was placed on top of AlCl3. The function of the glass
wool layer was to prevent Al2O3 impurities from rising with the sublimate and
contaminating it. The sublimation was done on the high vacuum line overnight at
~85 °C. Sublimed AlCl3 (~ 4.5 g) was collected in the glove box and stored in an
amber vial in the box until further use.
2.5.2. Synthesis of [PCl2N]3.AlCl3
In the glove box, [PCl2N]3 (0.69 g, 2.0 mmol) was dissolved in hexane (~
20 mL) to give a colorless solution. AlCl3 (0.27 g, 2.0 mmol) was added and
colorless crystals instantly formed on the wall of the flask. Due to light-sensitivity
of the solution, the reaction flask was wrapped in aluminum foil and stored in the
dark for 10 days as more crystals grew. The solution was filtered to collect the
first batch of crystals, which were characterized to be [PCl2N]3.AlCl3. Yield: ~89%.
11
MP: 128-130 °C. 31P NMR (CDCl3) at 0 °C: δ 26.8 ppm (d), 16.6 ppm (t). See the
Appendix for X-ray crystallographic information.
2.6. Interaction of [PCl2N]3 with AlBr3
In order to avoid protonated impurities, high vacuum line and glove box
techniques were used instead of the Schlenk line. Because the [PCl2N]3.AlBr3
adduct was light sensitive, exposure to light was minimized throughout all
phases of the work.
2.6.1. Purification of AlBr3
The sealed glass ampoule container of AlBr3 was scored open in the glove
box. AlBr3 (5 g) was put in a sublimator and sublimation was conducted on the
high vacuum line overnight at ~ 70 °C. Sublimed AlBr3 (4.8 g) was collected in
the glove box and stored in an amber vial in the box.
2.6.2. Synthesis of [PCl2N]3.AlBr3
In the glove box, [PCl2N]3 (0.69 g, 2.0 mmol) was dissolved in hexane (~
20 mL) to give a colorless solution. AlBr3 (0.53 g, 2.0 mmol) was added and the
flask was swirled. The solution turned cloudy and needle-like colorless crystals
formed on the wall of the flask. Due to light-sensitivity of the solution, the reaction
flask was wrapped in aluminum foil and stored in the dark for 7 days. The
volatiles were slowly removed with the reaction flask chilled in a methanol/ice
slush bath. The crystals were characterized to be [PCl2N]3.AlBr3. Yield: ~87%.
12
MP: 174-175 °C. 31P NMR (CDCl3) at 0 °C: δ 26.7 ppm (d), 16.7 ppm (t). See the
Appendix for X-ray crystallographic information.
2.7. Interaction of [PCl2N]3 with GaCl3
In order to avoid protonated impurities, high vacuum line and glove box
techniques were used instead of the Schlenk line. Because the PCl2N]3.GaCl3
adduct was light sensitive, exposure to light was minimized throughout all
phases of the work.
2.7.1. Purification of GaCl3
The sealed glass ampoule containing GaCl3 was scored open in the glove
box. GaCl3 (5 g) was placed in a sublimator. The overnight sublimation
conducted on the high vacuum line at 45 °C afforded 4.5 g of pure GaCl3. The
sublimate was collected in the glove box and stored in an amber vial in the box
until use.
2.7.2. Synthesis of [PCl2N]3.GaCl3
In the glove box, [PCl2N]3 (0.69 g, 2.0 mmol) was dissolved in hexane (~
20 mL) to give a colorless solution. GaCl3 (0.35 g, 2.0 mmol) was added. The
flask was swirled and all dissolved. Due to light-sensitivity of the solution, the
reaction flask was wrapped in aluminum foil and stored in the dark for 2 days.
The volatiles were slowly removed and colorless crystals were collected. The
product was characterized to be [PCl2N]3.GaCl3. Yield: ~83%. MP: 126-127 °C.
13
31
P NMR (CDCl3) at -55 °C: δ 25.28 ppm (d), δ 16.08 ppm (t). See the Appendix
for X-ray crystallographic information.
2.8. Interaction of [PCl2N]3 with BCl3
In the glove box, [PCl2N]3 (0.49 g, 1.5 mmol) was put in a Schlenk flask.
BCl3 solution in heptane (1M, 1.5 mL, 1.5 mmol) was added via syringe. With the
reaction mixture being stirred constantly, hexane was added drop-wise until all of
the solids dissolved. The flask was wrapped in aluminum foil and stored in the
dark for 7 days. The volatiles were slowly removed to give colorless crystals
which were characterized to be the starting material, [PCl2N]3. 31P NMR (CDCl3):
δ 20.0 ppm (s).
2.9. Interaction of [PCl2N]3 with BBr3
In the glove box, [PCl2N]3 (0.34 g, 1.1 mmol) was dissolved in hexane (~
20 mL). BBr3 (1M, 1.1 mL, 1.1 mmol) was added via syringe. The reaction flask
was swirled to mix the contents. No change was observed. The flask was
wrapped in aluminum foil and stored in the dark for 30 minutes. Clear, colorless
crystals formed on the wall of the flask. The flask was stored in the dark for 7
days to promote crystal growth. X-ray crystallographic characterization of the
crystals showed that they were the starting material, [PCl2N]3. 31P NMR (CDCl3):
δ 20.0 ppm (s).
14
2.10. Interaction of [PCl2N]3 with InCl3
In the glove box, InCl3 (0.44 g, 2.0 mmol) was put in a Schlenk flask
containing hexane (~ 20 mL). InCl3 did not dissolve in hexane. [PCl2N]3 (0.69 g,
2.0 mmol) was added and the flask was wrapped in aluminum foil. The reaction
mixture was stirred overnight. The volatiles were slowly removed under vacuum.
The resulting white solid was characterized to be the starting material, [PCl2N]3.
31
P NMR (CDCl3): δ 20.0 ppm (s).
15
CHAPTER III
RESULTS AND DISCUSSION
As stated in the introduction, even though several interactions of Lewis
acids with [PCl2N]3 had previously been reported, the products were poorly
characterized by modern standards and their structures were not agreed upon.
The focus of this research was to synthesize complexes of [PCl2N]3 with Lewis
acids of interest and to characterize the products using modern techniques that
were not common at the times of previous reports, most importantly by using VT
NMR studies.
3.1. Interactions of [PCl2N]3 with Lewis acids
Cl Cl
P
N
N
Cl
Cl
P
P
Cl N Cl
Cl
MX3
hexane
Cl
MX3
N
N
Cl
Cl
P
P
Cl
N Cl
MX3= AlCl3, AlBr3or GaCl3
P
(Eq. 3.1)
The 1:1 reaction of [PCl2N]3 with Lewis acids AlCl3, AlBr3 and GaCl3 can
be described by the equation 3.1. [PCl2N]3.AlCl3 adducts are plate-like crystals
with the melting point 128-130 °C. [PCl2N]3.AlBr3 adducts are needle-like crystals
and have the melting point 174-175 °C. The melting point of [PCl2N]3.AlBr3 was
previously reported to be 174 °C.5 [PCl2N]3.GaCl3 adducts are needle-like
crystals having the melting point 126-127 °C.
16
The adducts were extremely moisture sensitive, and protonated impurities
tended to develop. Vigorous anaerobic techniques were required in all stages of
handling. Exposure to light needed to be limited, especially in solutions of
chloronated hydrocarbons.
The reactions of [PCl2N]3 with BCl3, BBr3 and InCl3 did not give adducts.
This means that the nitrogen atoms on [PCl2N]3 are very poor bases and that
only the interactions with very strong Lewis acids lead to adduct formations.
3.2. X-ray crystallography
The crystals of the [PCl2N]3.AlCl3, [PCl2N]3.AlBr3 and [PCl2N]3.GaCl3
adducts suitable for single crystal x-ray diffraction analysis were grown from dry
hexane.
3.2.1. [PCl2N]3.AlCl3 adduct
The thermal ellipsoid plot of [PCl2N]3.AlCl3 can be seen in Figure 3.1. The
asymmetric unit of [PCl2N]3.AlCl3 contains half of two molecules and an aluminum
atom was bound to one nitrogen atom on each molecule. The bond lengths of AlN pairs are 1.982(3) Å and 1.970(3) Å. The bond distances between the nitrogen
atom that is bound to the aluminum atom and the two neighboring phosphorous
atoms are 1.6521(14) Å and 1.6530(14) Å. These bond distances are longer than
the P-N bonds in the starting material [PCl2N]317 and they show single bond
character. The remaining P-N bond distances of the adduct fall between 1.560(2)
Å and 1.573(2) Å and they are comparable to the P-N bonds of [PCl2N]3.17
17
18
Figure 3.1. Thermal Ellipsoid Plot of [PCl2N]3.AlCl3
3.2.2. [PCl2N]3.AlBr3 adduct
The thermal ellipsoid plot of [PCl2N]3.AlBr3 is shown in Figure 3.2. There is
no halogen exchange between AlBr3 and [PCl2N]3. The asymmetric unit contains
half of two [PCl2N]3.AlBr3 molecules and an aluminum atom was bound to one
nitrogen atom on each molecule. The bond lengths of Al-N pairs are 1.994(3) Å
and 1.992(3) Å. The bond distances between the nitrogen atom that is bound to
the aluminum atom and the two neighboring phosphorous atoms are 1.6532(15)
Å and 1.6517(15) Å. These bond distances are longer than the P-N bonds in the
starting material [PCl2N]317 and they show single bond character. The remaining
P-N bond distances of the adduct fall between 1.562(2) Å and 1.577(2) Å and
they are comparable to the P-N bonds of [PCl2N]3.17
19
20
Figure 3.2. Thermal Ellipsoid Plot of [PCl2N]3.AlBr3
3.2.3. [PCl2N]3.GaCl3 adduct
The thermal ellipsoid plot of [PCl2N]3.GaCl3 is shown in Figure 3.3. The
asymmetric unit contains two [PCl2N]3.GaCl3 molecules and a gallium atom was
bound to one nitrogen atom on each molecule (Figure 3.4). The bond lengths of
Al-N pairs are 1.994(3) Å and 1.992(3) Å. The bond distances between the
nitrogen atom that is bound to the gallium atom and the two neighboring
phosphorous atoms are 1.6532(15) Å and 1.6517(15) Å. These bond distances
are longer than the P-N bonds in the starting material [PCl2N]317 and they show
single bond character. The remaining P-N bond distances of in the adduct fall
between 1.562(2) Å and 1.577(2) Å and they are comparable to the P-N bonds of
[PCl2N]3.17
21
Figure 3.3. Thermal Ellipsoid Plot of [PCl2N]3.GaCl3
22
23
Figure 3.4. Thermal Ellipsoid Plot of the Asymmetric Unit of [PCl2N]3.GaCl3
3.3. NMR Studies
The 31P spectra of [PCl2N]3.AlCl3, [PCl2N]3.AlBr3, and [PCl2N]3.GaCl3
obtained in CDCl3 at 25 °C are shown in Figure 3.5. It can be seen in the spectra
that all three adducts are fluxional at this temperature. In order to better
understand the fluxional nature, VT NMR studies of the adducts were performed
in CDCl3.
24
25
Figure 3.5. 31P NMR Spectra of [PCl2N]3.AlCl3, [PCl2N]3.AlBr3, and [PCl2N]3.GaCl3 in CDCl3 at 25 °C
3.3.1. VT NMR of [PCl2N]3.AlCl3
31
P VT NMR spectra of [PCl2N]3.AlCl3 in CDCl3 were obtained at 55 °C, 40
°C, 30 °C, 0 °C, and -20 °C. Two single resonances were observed at 27.5 ppm
and 17.3 ppm at 55 °C (Figure 3.16) and 17.2 ppm and 17.0 ppm for 40 °C
(Figure 3.17). At 30 °C, the resonance at 27.3 ppm had resolved into a doublet.
However, the resonance at 16.9 ppm had not resolved into a triplet yet, although
it did have two side shoulders (Figure 3.18). At 0 °C, a well resolved doublet at
26.8 ppm and a triplet at 16.6 ppm were observed, along with a singlet at 18.9
ppm (Figure 3.19). At -20 ppm, the doublet was seen at 26.5 ppm, where as the
triplet was at 16.4 ppm and the singlet was at 18.7 ppm. The singlet was due to
protonated impurities in the product (Figure 3.20). Similar resonance had been
observed in the reaction of [PCl2N]3 and AlBr3 in the presence of water.13
H VT NMR spectra of the [PCl2N]3.AlCl3 in CDCl3 were also obtained at
1
40 °C, 30 °C, 0 °C, and -20 °C. A singlet was observed at 10.1 ppm at all
temperatures studied (Figure 3.21). The presence of the singlet in this ppm
region confirmed our hypothesis that there were protonated impurities in the
product.
26
27
Figure 3.6. 31P NMR Spectrum of [PCl2N]3.AlCl3 in CDCl3 at 55 °C
28
Figure 3.7. 31P NMR Spectrum of [PCl2N]3.AlCl3 in CDCl3 at 40 °C
29
Figure 3.8. 31P NMR Spectrum of [PCl2N]3.AlCl3 in CDCl3 at 30 °C
30
Figure 3.9. 31P NMR Spectrum of [PCl2N]3.AlCl3 in CDCl3 at 0 °C
31
Figure 3.10. 31P NMR Spectrum of [PCl2N]3.AlCl3 in CDCl3 at -20 °C
32
Figure 3.11. 1H NMR Spectra of [PCl2N]3.AlCl3 in CDCl3 at 40 °C, 30 °C, 0 °C, and -20 °C
3.3.2. VT NMR of [PCl2N]3.AlBr3
P VT NMR of [PCl2N]3.AlBr3 in CDCl3 were obtained at 25 °C, 0 °C, -20
31
°C, and -40 °C. At 25 °C, two single resonances at 27.1 ppm and 16.9 ppm were
observed (Figure 3.22). At 0 °C, the resonance at 26.7 ppm had resolved into a
doublet. However, the resonance at 16.7 ppm had not resolved into a triplet yet,
although it did have two side shoulders. A small broad feature was also seen at
the base of this resonance (Figure 3.23). At -20 °C, a well resolved doublet at
26.5 ppm and a triplet at 16.5 ppm were observed, along with a singlet at 17.6
ppm (Figure 3.24). At -40 ppm, the doublet was seen at 26.2 ppm, where as the
triplet was at 16.2 ppm and the singlet was at 17.3 ppm. The singlet was due to
protonated impurities in the product (Figure 3.25). Similar resonance had been
observed in the reaction of [PCl2N]3 and AlBr3 in the presence of water.13
H VT NMR spectra of [PCl2N]3.AlBr3 in CDCl3 were also obtained at 25
1
°C, 0 °C, -20 °C, and -40 °C (Figure 3.26). At 25 °C and 0 °C, a singlet was
observed at 9.4 ppm. At -20 °C and -40 °C, the resonance had moved to 9.3 ppm
and 9.2 ppm respectively. The presence of the singlet in this ppm region
confirmed our hypothesis that there were protonated impurities in the product.
33
34
Figure 3.12. 31P NMR Spectrum of [PCl2N]3.AlBr3 in CDCl3 at 25 °C
35
Figure 3.13. 31P NMR Spectrum of [PCl2N]3.AlBr3 in CDCl3 at 0 °C
36
Figure 3.14. 31P NMR Spectrum of [PCl2N]3.AlBr3 in CDCl3 at -20 °C
37
Figure 3.15. 31P NMR Spectrum of [PCl2N]3.AlBr3 in CDCl3 at -40 °C
38
Figure 3.16. 1H NMR Spectra of [PCl2N]3.AlBr3 in CDCl3 at 25 °C, 0 °C, -20 °C, and -40 °C
3.3.3. VT NMR of [PCl2N]3.GaCl3
31
P VT NMR spectra of [PCl2N]3.GaCl3 in CDCl3 were obtained at
35 °C, 30 °C, 25 °C, 15 °C, 0 °C, -20 °C, -40 °C, -50 °C, and -55 °C. At 35 °C,
the exchange was very rapid and a sharp singlet was observed at 22.1 ppm
(Figure 3.6). At 30 °C (Figure 3.7), 25 °C (Figure 3.8), and 15 °C (Figure 3.9), a
gradually broader singlet at 22.9 ppm, 23.9 ppm, and 23.7 ppm were observed
respectively. At 0 °C (Figure 3.10), two single resonances were observed at 26.2
ppm and 17.1 ppm. At -20 °C (Figure 3.11), the two resonances became sharper
(25.6 ppm and 16.5 ppm), but the individual peaks were still not resolved. At -40
°C, the resonance at 25.4 ppm had taken the form of a doublet. Although the
resonance at 16.2 ppm had developed two shoulders, it had not resolved into a
triplet. A new peak at 19.8 ppm was also observed at this temperature (Figure
3.12). At -50 °C (Figure 3.13) and -55 °C (Figure 3.14), a doublet at 25.3 ppm a
singlet at 19.7 ppm, and a triplet at 16.1 ppm were observed. The singlet appears
to be due to protonated impurities in the product. Similar resonance had been
observed in the reaction of [PCl2N]3 and AlBr3 in the presence of water.13
H VT NMR spectra of [PCl2N]3.GaCl3 in CDCl3 were also obtained at 35
1
°C, 30 °C, 25 °C, 15 °C, 0 °C, -20 °C, -40 °C, -50 °C, and -55 °C. A singlet was
observed at 9.8 ppm for all temperatures. However the peak became sharper as
the temperature decreased (Figure 3.15). The presence of the singlet in this
ppm region confirmed our hypothesis that there were protonated impurities in the
product.
39
40
Figure 3.17. 31P NMR Spectrum of [PCl2N]3.GaCl3 in CDCl3 at 35 °C
41
Figure 3.18. 31P NMR Spectrum of [PCl2N]3.GaCl3 in CDCl3 at 30 °C
42
Figure 3.19. 31P NMR Spectrum of [PCl2N]3.GaCl3 in CDCl3 at 25 °C
43
Figure 3.20. 31P NMR Spectrum of [PCl2N]3.GaCl3 in CDCl3 at 15 °C
44
Figure 3.21. 31P NMR Spectrum of [PCl2N]3.GaCl3 in CDCl3 at 0 °C
45
Figure 3.22. 31P NMR Spectrum of [PCl2N]3.GaCl3 in CDCl3 at -20 °C
46
Figure 3.23. 31P NMR Spectrum of [PCl2N]3.GaCl3 in CDCl3 at -40 °C
47
Figure 3.24. 31P NMR Spectrum of [PCl2N]3.GaCl3 in CDCl3 at -50 °C
48
Figure 3.25. 31P NMR Spectrum of [PCl2N]3.GaCl3 in CDCl3 at -55 °C
49
Figure 3.26. 1H NMR Spectra of [PCl2N]3.GaCl3 in CDCl3 at -55 °C, -50 °C, -40 °C, -20 °C, 0 °C,
15 °C, 25 °C and 30 °C
3.4. Comparison of [PCl2N]3.AlCl3, [PCl2N]3.AlBr3 and [PCl2N]3.GaCl3
The x-ray crystallographic data of all three adducts show that the P-N
bonds containing the nitrogen atom that is bound to the Lewis acids are longer
than the rest of the P-N bonds in the ring. This lengthening, and therefore
weakening, of the ring bonds due to the adduct formation might facilitate bond
breakage in the ROP process. The bond distances between Al-N (1.970(3) Å 1.994(3) Å) and Ga-N (2.040(3) Å -2.048(3) Å) are comparable to the dative bond
distances between nitrogen and group 13 metals.12, 13 The Al-N distance in
[PCl2N]3.AlCl3 is shorter that that in [PCl2N]3.AlBr3. This suggests that AlCl3 binds
more tightly than AlBr3 does to [PCl2N]3.
In comparing the 31P NMR spectra of [PCl2N]3.AlCl3, [PCl2N]3.AlBr3, and
[PCl2N]3.GaCl3, it was seen that the rate of the exchange process was not the
same for all three adducts. The expected doublet and triplet resonances were
well resolved at 0 °C for [PCl2N]3.AlCl3, and at -20 °C for [PCl2N]3.AlBr3. For
[PCl2N]3.GaCl3, however, it was not until -50 °C that the expected peaks became
resolved. This indicates that the rate of exchange of [PCl2N]3.GaCl3 is faster than
those of [PCl2N]3.AlCl3 and [PCl2N]3.AlBr3. The peaks did not coalesce in 31P
NMR spectra for [PCl2N]3.AlCl3 and [PCl2N]3.AlBr3 even at the boiling point
temperature of CDCl3. Therefore, VT NMR studies need to be done in a solvent
that has a higher boiling point than CDCl3, in order to calculate the rate of
exchange of [PCl2N]3.AlCl3 and [PCl2N]3.AlBr3 adducts. From 1H VT NMR spectra
of the three adducts, the singlet was observed more and more down-field going
from [PCl2N]3.AlBr3 to [PCl2N]3.GaCl3 and [PCl2N]3.AlCl3. Therefore, the acidities
50
of the protonated impurities in the adducts can be ranked in the increasing order
from [PCl2N]3.AlBr3 to [PCl2N]3.GaCl3 and [PCl2N]3.AlCl3.
51
CHAPTER IV
CONCLUSION
Adducts of [PCl2N]3 with AlCl3, AlBr3, and GaCl3 were successfully
synthesized and characterized by X-ray crystallography and 31P and 1H VT NMR.
The adducts assume the structure of the variant 1 depicted in Figure 1.2. The
adduct formation lengthens the bonds between the nitrogen atom that is
interacting with the Lewis acid and its two phosphorous neighbors in the ring.
Because this bond weakening might promote the bond breakage in the initial
step of the ROP of [PCl2N]3, potential catalytic abilities of these adducts in the
ROP process should be explored.
The [PCl2N]3.AlCl3, [PCl2N]3.AlBr3, [PCl2N]3.GaCl3 adducts are light
sensitive, especially in solutions of chloronated hydrocarbons. The adducts are
also extremely moisture sensitive, and vigorous anaerobic techniques are
required in order to prevent the formation of protonated impurities. The
involvement of these protonated species both in the ROP process and in the
gradual degradation of the chlorophosphazene polymer in storage needs to be
studied.
The exchange process in solution for all three adducts were investigated
using 1H and 31P VT NMR studies. At 0 °C, the resonance peaks in the 31P NMR
52
spectra of [PCl2N]3.AlCl3 and [PCl2N]3.AlBr3 resolve into the expected pattern
consisting of one doublet and one triplet. In the 31P NMR spectra of
[PCl2N]3.GaCl3, the resonance peaks resolve into a doublet and a triplet at -50
°C. The fact that the resonances for [PCl2N]3.GaCl3 resolve at lower temperature
than [PCl2N]3.AlCl3 and [PCl2N]3.AlBr3 indicates that the exchange in
[PCl2N]3.GaCl3 is faster than that in [PCl2N]3.AlCl3 and [PCl2N]3.AlBr3. In 31P NMR
spectra of [PCl2N]3.AlCl3 and [PCl2N]3.AlBr3, the peaks do not coalesce at the
boiling point temperature of CDCl3. Therefore, in order to calculate the rates of
exchange of these adducts, VT NMR studies need to be done in a solvent that
has a higher boiling temperature than CDCl3.
Of the interactions studied, the reactions of [PCl2N]3 with BCl3, BBr3 and
InCl3 did not lead to adduct formation. This indicates that the nitrogen atoms on
[PCl2N]3 are very poor bases and that very strong Lewis acids are needed to
form adducts. The interactions of [PCl2N]3 with other strong Lewis acids involving
both main group and transition metals should be studied.
53
REFERENCES
(1) de Jaeger, R.; Gleria, M. Progress in Polymer Science 1998, 23, 179-276.
(2) Allcock, H. R. Chemistry and Applications of Polyphosphazenes; WileyInterscience: New York, 2003; pp 109-187.
(3) Emsley, J.; Udy, P. B. Polymer, 1972, 13, 593-594.
(4) Allcock, H. R. Phosphorous-Nitrogen Compounds; Academic Press: New
York, 1972; pp 230-248.
(5) Coxon, G. E.; Sowerb, D. B. Journal of the Chemical Society A: Inorganic,
Physical, Theoretical 1969, 1969, 3012-3014.
(6) Kravchenko, E. A.; Levin, B. V.; Bananyarly, S. I.; Toktomatov, T. A. Koord.
Khim. 1977, 3, 374-379.
(7) Sennett, M. S.; Hagnauer, G. L.; Singler, R. E.; Davies, G. Macromolecules
1986, 19, 959-964.
(8) Potts, M. K.; Hagnauer, G. L.; Sennett, M. S.; Davies, G. Macromolecules
1989, 22, 4235-4239.
(9) Schacht, E.; Vandorpe, J.; Dejardin, S.; Lemmouchi, Y.; Seymour, L.
Biotechnology and bioengineering 1996, 52, 102-108.
(10) Bode, H.; Bütow, K.; Lienau, G. Chem. Ber 1948, 81, 547-552.
(11) Rivard, E.; Lough, A. J.; Chivers, T.; Manners, I. Inorg. Chem. 2004, 43,
802-811.
(12) Heston, A. J.; Panzner, M. J.; Youngs, W. J.; Tessier, C. A. Inorg. Chem.
2005, 44, 6518-6520.
(13) Heston, A. J.; Tessier, C. A.; Panzner, M. J.; Youngs, W. J. Phosphorus,
Sulfur Silicon Relat. Elem. 2004, 179, 831-837.
(14) Shriver, D. F.; Drexdon, M. A. The Manipulation of Air-Sensitive
Compounds; Wiley: New York, 1986.
54
(15) Plesch, P. H. High Vacuum Techniques for Chemical Syntheses and
Measurement ; Cambridge University Press: New York, 1989.
(16) Sanderson, R. T. Vacuum Manipulation of Volatile Compounds; John Wiley
& Sons: New York, 1948.
(17) Allcock, H. R. Chem. Rev. 1972, 72, 315-356.
55
APPENDIX
SUPPLEMENTARY MATERIALS FOR ALL X-RAY CRYSTAL STRUCTURES
Adduct: [PCl2N]3.AlCl3
56
Table 1. Crystal data and structure refinement for [PCl2N]3.AlCl3.
Empirical formula
Al Cl9 N3 P3
Formula weight
480.97
Temperature
100(2) K
Wavelength
0.71073 Å
Crystal system
Orthorhombic
Space group
Pmn2(1)
Unit cell dimensions
a = 11.992(2) Å
= 90°
b = 11.713(2) Å
= 90°
c = 10.7730(19) Å
= 90°
Volume
1513.3(5) Å3
Z
4
Density (calculated)
2.111 Mg/m3
Absorption coefficient
2.014 mm-1
F (000)
928
Crystal size
0.27 x 0.10 x 0.04 mm3
Theta range for data collection
1.74 to 28.24°.
Index ranges
-15<=h<=15, -15<=k<=15, -14<=l<=14
Reflections collected
12759
Independent reflections
3732 [R (int) = 0.0259]
Completeness to theta = 28.24°
97.5 %
Absorption correction
Semi-empirical from equivalents
Max. and min. transmission
0.923 and 0.733
Refinement method
Full-matrix least-squares on F2
Data / restraints / parameters
3732 / 1 / 163
Goodness-of-fit on F2
1.093
Final R indices [I>2sigma(I)]
R1 = 0.0226, wR2 = 0.0526
R indices (all data)
R1 = 0.0234, wR2 = 0.0529
Absolute structure parameter
0.15(6)
Largest diff. peak and hole
0.417 and -0.260 e.Å-3
57
Table 2. Atomic coordinates (x 104) and equivalent isotropic displacement
parameters (Å2x 103) for [PCl2N]3.AlCl3. U(eq) is defined as one third of the
trace of the orthogonalized Uij tensor.
_____________________________________________________________________________
x
y
z
U(eq)
_____________________________________________________________________________
Cl(1)
0
1326(1)
6532(1)
34(1)
Cl(2)
0
3284(1)
4612(1)
26(1)
Cl(3)
1830(1)
-1227(1)
3813(1)
26(1)
Cl(4)
2241(1)
673(1)
1838(1)
26(1)
Cl(5)
0
357(1)
-537(1)
33(1)
Cl(6)
1442(1)
-1990(1)
744(1)
27(1)
Cl(7)
1789(1)
3953(1)
7399(1)
22(1)
Cl(8)
2268(1)
6488(1)
8100(1)
22(1)
Cl(9)
0
3019(1)
10894(1)
40(1)
Cl(10)
0
5414(1)
12106(1)
23(1)
Cl(11)
0
8278(1)
6680(1)
20(1)
Cl(12)
1423(1)
6085(1)
5095(1)
24(1)
P(1)
0
1599(1)
4725(1)
17(1)
P(2)
1179(1)
184(1)
3117(1)
16(1)
P(3)
1176(1)
5261(1)
8347(1)
15(1)
P(4)
0
4673(1)
10469(1)
17(1)
Al(1)
0
-963(1)
798(1)
18(1)
Al(2)
0
6552(1)
6125(1)
14(1)
N(1)
0
-153(2)
2414(2)
15(1)
N(2)
1108(2)
1124(2)
4141(2)
27(1)
N(3)
0
5657(2)
7673(2)
14(1)
N(4)
1110(2)
4966(2)
9757(2)
23(1)
_____________________________________________________________________________
58
Table 3. Bond lengths [Å] and angles [°] for [PCl2N]3.AlCl3.
_____________________________________________________
Cl(1)-P(1)
1.9730(12)
Cl(2)-P(1)
1.9772(12)
Cl(3)-P(2)
1.9748(8)
Cl(4)-P(2)
1.9625(8)
Cl(5)-Al(1)
2.1118(13)
Cl(6)-Al(1)
2.1077(8)
Cl(7)-P(3)
1.9827(8)
Cl(8)-P(3)
1.9620(8)
Cl(9)-P(4)
1.9907(13)
Cl(10)-P(4)
1.9660(11)
Cl(11)-Al(2)
2.1089(12)
Cl(12)-Al(2)
2.1082(8)
P(1)-N(2)#1
1.572(2)
P(1)-N(2)
1.572(2)
P(2)-N(2)
1.561(2)
P(2)-N(1)
1.6521(14)
P(3)-N(4)
1.560(2)
P(3)-N(3)
1.6530(14)
P(4)-N(4)#1
1.573(2)
P(4)-N(4)
1.573(2)
Al(1)-N(1)
1.982(3)
Al(1)-Cl(6)#1
2.1077(8)
Al(2)-N(3)
1.970(3)
Al(2)-Cl(12)#1
2.1082(8)
N(1)-P(2)#1
1.6521(14)
N(3)-P(3)#1
1.6530(14)
N(2)#1-P(1)-N(2)
115.42(15)
N(2)#1-P(1)-Cl(1)
109.74(9)
N(2)-P(1)-Cl(1)
109.74(9)
N(2)#1-P(1)-Cl(2)
109.17(9)
N(2)-P(1)-Cl(2)
109.17(9)
Cl(1)-P(1)-Cl(2)
102.84(5)
59
Table 3. Bond lengths [Å] and angles [°] for [PCl2N]3.AlCl3 (continued).
N(2)-P(2)-N(1)
116.51(11)
N(2)-P(2)-Cl(4)
108.97(9)
N(1)-P(2)-Cl(4)
107.63(9)
N(2)-P(2)-Cl(3)
110.11(9)
N(1)-P(2)-Cl(3)
108.20(9)
Cl(4)-P(2)-Cl(3)
104.75(4)
N(4)-P(3)-N(3)
116.50(11)
N(4)-P(3)-Cl(8)
109.22(8)
N(3)-P(3)-Cl(8)
107.72(9)
N(4)-P(3)-Cl(7)
110.42(8)
N(3)-P(3)-Cl(7)
107.84(9)
Cl(8)-P(3)-Cl(7)
104.43(4)
N(4)#1-P(4)-N(4)
115.50(15)
N(4)#1-P(4)-Cl(10)
109.94(8)
N(4)-P(4)-Cl(10)
109.94(8)
N(4)#1-P(4)-Cl(9)
108.91(8)
N(4)-P(4)-Cl(9)
108.91(8)
Cl(10)-P(4)-Cl(9)
102.88(5)
N(1)-Al(1)-Cl(6)#1
107.31(5)
N(1)-Al(1)-Cl(6)
107.31(5)
Cl(6)#1-Al(1)-Cl(6)
110.29(5)
N(1)-Al(1)-Cl(5)
104.35(9)
Cl(6)#1-Al(1)-Cl(5)
113.51(4)
Cl(6)-Al(1)-Cl(5)
113.51(4)
N(3)-Al(2)-Cl(12)#1
107.91(5)
N(3)-Al(2)-Cl(12)
107.91(5)
Cl(12)#1-Al(2)-Cl(12)
108.10(5)
N(3)-Al(2)-Cl(11)
105.69(9)
Cl(12)#1-Al(2)-Cl(11)
113.47(3)
Cl(12)-Al(2)-Cl(11)
113.47(3)
P(2)-N(1)-P(2)#1
117.68(16)
P(2)-N(1)-Al(1)
121.15(8)
P(2)#1-N(1)-Al(1)
121.15(8)
60
Table 3. Bond lengths [Å] and angles [°] for [PCl2N]3.AlCl3 (continued).
P(2)-N(2)-P(1)
125.33(13)
P(3)-N(3)-P(3)#1
117.18(15)
P(3)-N(3)-Al(2)
121.41(8)
P(3)#1-N(3)-Al(2)
121.41(8)
P(3)-N(4)-P(4)
124.48(13)
_____________________________________________________________
Symmetry transformations used to generate equivalent atoms:
#1 -x,y,z
61
Table 4. Anisotropic displacement parameters (Å2x 103) for [PCl2N]3.AlCl3. The
anisotropic displacement factor exponent takes the form: -2 2[ h2 a*2U11 + ... +
2 h k a* b* U12 ]
_____________________________________________________________________________
U11
U22
U33
U23
U13
U12
_____________________________________________________________________________
Cl(1)
68(1)
20(1)
14(1)
1(1)
0
0
Cl(2)
41(1)
18(1)
19(1)
1(1)
0
0
Cl(3)
26(1)
29(1)
22(1)
3(1)
-5(1)
7(1)
Cl(4)
23(1)
27(1)
30(1)
-1(1)
9(1)
-7(1)
Cl(5)
61(1)
24(1)
14(1)
3(1)
0
0
Cl(6)
29(1)
25(1)
27(1)
-8(1)
7(1)
5(1)
Cl(7)
24(1)
20(1)
23(1)
-5(1)
-3(1)
7(1)
Cl(8)
16(1)
24(1)
25(1)
-4(1)
1(1)
-5(1)
Cl(9)
70(1)
17(1)
33(1)
5(1)
0
0
Cl(10)
31(1)
24(1)
14(1)
-1(1)
0
0
Cl(11)
20(1)
14(1)
28(1)
-2(1)
0
0
Cl(12)
27(1)
26(1)
20(1)
3(1)
9(1)
7(1)
P(1)
21(1)
18(1)
12(1)
-4(1)
0
0
P(2)
14(1)
19(1)
15(1)
-4(1)
0(1)
0(1)
P(3)
13(1)
17(1)
14(1)
-1(1)
0(1)
1(1)
P(4)
21(1)
16(1)
14(1)
1(1)
0
0
Al(1)
25(1)
16(1)
12(1)
-2(1)
0
0
Al(2)
16(1)
14(1)
13(1)
0(1)
0
0
N(1)
14(1)
18(1)
14(1)
-4(1)
0
0
N(2)
18(1)
34(1)
29(1)
-19(1)
-5(1)
1(1)
N(3)
12(1)
17(1)
14(1)
1(1)
0
0
N(4)
15(1)
35(1)
19(1)
5(1)
-3(1)
5(1)
62
Adduct: [PCl2N]3.AlBr3
63
Table 5. Crystal data and structure refinement for [PCl2N]3.AlBr3.
Empirical formula
Al2 Br6 Cl12 N6 P6
Formula weight
1228.71
Temperature
100(2) K
Wavelength
0.71073 Å
Crystal system
Monoclinic
Space group
P2(1)/m
Unit cell dimensions
a = 10.8919(12) Å
= 90°
b = 12.1067(14) Å
= 91.898(2)°
c = 12.1387(14) Å
= 90°
Volume
1599.8(3) Å3
Z
4
Density (calculated)
2.551 Mg/m3
Absorption coefficient
8.898 mm-1
F (000)
1144
Crystal size
0.15 x 0.07 x 0.03 mm3
Theta range for data collection
1.68 to 28.28°.
Index ranges
-14<=h<=14, -15<=k<=16, -15<=l<=16
Reflections collected
13941
Independent reflections
3951 [R (int) = 0.0249]
Completeness to theta = 28.28°
95.1 %
Absorption correction
Semi-empirical from equivalents
Max. and min. transmission
0.766 and 0.547
Refinement method
Full-matrix least-squares on F2
Data / restraints / parameters
3951 / 0 / 163
Goodness-of-fit on F2
1.000
Final R indices [I>2sigma(I)]
R1 = 0.0220, wR2 = 0.0482
R indices (all data)
R1 = 0.0283, wR2 = 0.0503
Largest diff. peak and hole
0.574 and -0.457 e.Å-3
64
Table 6. Atomic coordinates (x 104) and equivalent isotropic displacement
parameters (Å2x 103) for [PCl2N]3.AlBr3. U(eq) is defined as one third of the
trace of the orthogonalized Uij tensor.
_____________________________________________________________________________
__________________________x___________y____________z_____________U(eq)________
Br(1)
55(1)
9005(1)
3832(1)
20(1)
Br(2)
1831(1)
7500
1634(1)
18(1)
Br(3)
4138(1)
4017(1)
-1936(1)
20(1)
Br(4)
5615(1)
2500
511(1)
21(1)
P(1)
3418(1)
8664(1)
4696(1)
12(1)
P(2)
5531(1)
7500
5268(1)
13(1)
P(3)
1912(1)
1331(1)
362(1)
14(1)
P(4)
434(1)
2500
1779(1)
17(1)
Al(1)
1186(1)
7500
3390(1)
13(1)
Al(2)
4114(1)
2500
-834(1)
14(1)
N(1)
4828(2)
8602(2)
4966(2)
16(1)
N(2)
2740(2)
7500
4305(2)
13(1)
N(3)
1025(2)
1400(2)
1346(2)
23(1)
N(4)
2572(2)
2500
4(2)
12(1)
Cl(1)
2547(1)
9241(1)
5982(1)
22(1)
Cl(2)
3109(1)
9752(1)
3526(1)
18(1)
Cl(3)
5945(1)
7500
6885(1)
20(1)
Cl(4)
7138(1)
7500
4584(1)
20(1)
Cl(5)
1049(1)
713(1)
-954(1)
23(1)
Cl(6)
3225(1)
274(1)
738(1)
21(1)
Cl(7)
511(1)
2500
3402(1)
29(1)
Cl(8)
-1358(1)
2500
1438(1)
31(1)
_____________________________________________________________________________
65
Table 7. Bond lengths [Å] and angles [°] for [PCl2N]3.AlBr3.
_____________________________________________________
Br(1)-Al(1)
2.2737(6)
Br(2)-Al(1)
2.2661(10)
Br(3)-Al(2)
2.2731(6)
Br(4)-Al(2)
2.2707(10)
P(1)-N(1)
1.562(2)
P(1)-N(2)
1.6532(15)
P(1)-Cl(2)
1.9575(8)
P(1)-Cl(1)
1.9791(8)
P(2)-N(1)#1
1.575(2)
P(2)-N(1)
1.575(2)
P(2)-Cl(4)
1.9622(12)
P(2)-Cl(3)
1.9988(12)
P(3)-N(3)
1.564(2)
P(3)-N(4)
1.6517(15)
P(3)-Cl(6)
1.9620(9)
P(3)-Cl(5)
1.9736(9)
P(4)-N(3)
1.577(2)
P(4)-N(3)#2
1.577(2)
P(4)-Cl(7)
1.9703(12)
P(4)-Cl(8)
1.9820(12)
Al(1)-N(2)
1.994(3)
Al(1)-Br(1)#1
2.2737(6)
Al(2)-N(4)
1.992(3)
Al(2)-Br(3)#2
2.2731(6)
N(2)-P(1)#1
1.6532(15)
N(4)-P(3)#2
1.6517(15)
N(1)-P(1)-N(2)
116.46(11)
N(1)-P(1)-Cl(2)
109.16(8)
N(2)-P(1)-Cl(2)
107.51(9)
N(1)-P(1)-Cl(1)
110.18(8)
N(2)-P(1)-Cl(1)
107.84(10)
Cl(2)-P(1)-Cl(1)
105.05(4)
66
Table 7. Bond lengths [Å] and angles [°] for [PCl2N]3.AlBr3 (continued).
N(1)#1-P(2)-N(1)
115.75(15)
N(1)#1-P(2)-Cl(4)
109.56(8)
N(1)-P(2)-Cl(4)
109.56(8)
N(1)#1-P(2)-Cl(3)
108.70(8)
N(1)-P(2)-Cl(3)
108.70(8)
Cl(4)-P(2)-Cl(3)
103.92(5)
N(3)-P(3)-N(4)
116.15(12)
N(3)-P(3)-Cl(6)
108.69(9)
N(4)-P(3)-Cl(6)
107.45(9)
N(3)-P(3)-Cl(5)
110.42(9)
N(4)-P(3)-Cl(5)
108.20(10)
Cl(6)-P(3)-Cl(5)
105.36(4)
N(3)-P(4)-N(3)#2
115.28(15)
N(3)-P(4)-Cl(7)
109.18(9)
N(3)#2-P(4)-Cl(7)
109.18(9)
N(3)-P(4)-Cl(8)
109.93(9)
N(3)#2-P(4)-Cl(8)
109.93(9)
Cl(7)-P(4)-Cl(8)
102.58(5)
N(2)-Al(1)-Br(2)
103.90(9)
N(2)-Al(1)-Br(1)#1
108.97(5)
Br(2)-Al(1)-Br(1)#1
114.16(3)
N(2)-Al(1)-Br(1)
108.97(5)
Br(2)-Al(1)-Br(1)
114.16(3)
Br(1)#1-Al(1)-Br(1)
106.52(4)
N(4)-Al(2)-Br(4)
103.42(9)
N(4)-Al(2)-Br(3)#2
109.06(5)
Br(4)-Al(2)-Br(3)#2
113.65(3)
N(4)-Al(2)-Br(3)
109.06(5)
Br(4)-Al(2)-Br(3)
113.65(3)
Br(3)#2-Al(2)-Br(3)
107.81(4)
P(1)-N(1)-P(2)
123.82(13)
P(1)-N(2)-P(1)#1
116.98(16)
P(1)-N(2)-Al(1)
121.51(8)
67
Table 7. Bond lengths [Å] and angles [°] for [PCl2N]3.AlBr3 (continued).
P(1)#1-N(2)-Al(1)
121.51(8)
P(3)-N(3)-P(4)
124.65(14)
P(3)-N(4)-P(3)#2
117.89(16)
P(3)-N(4)-Al(2)
121.06(8)
P(3)#2-N(4)-Al(2)
121.06(8)
_____________________________________________________________
Symmetry transformations used to generate equivalent atoms:
#1 x,-y+3/2,z
#2 x,-y+1/2,z
68
Table 8. Anisotropic displacement parameters (Å2x 103) for [PCl2N]3.AlBr3. The
anisotropic displacement factor exponent takes the form: -2 2[ h2 a*2U11 + ...
+ 2 h k a* b* U12 ]
_____________________________________________________________________________
U11
U22
U33
U23
U13
U12
_____________________________________________________________________________
Br(1)
15(1)
23(1)
22(1)
-5(1)
-1(1)
7(1)
Br(2)
20(1)
22(1)
12(1)
0
3(1)
0
Br(3)
21(1)
23(1)
17(1)
5(1)
2(1)
-4(1)
Br(4)
11(1)
36(1)
16(1)
0
-1(1)
0
P(1)
12(1)
11(1)
14(1)
0(1)
-1(1)
0(1)
P(2)
11(1)
13(1)
15(1)
0
-1(1)
0
P(3)
13(1)
14(1)
16(1)
1(1)
2(1)
-2(1)
P(4)
10(1)
26(1)
14(1)
0
3(1)
0
Al(1)
11(1)
16(1)
12(1)
0
0(1)
0
Al(2)
11(1)
19(1)
13(1)
0
2(1)
0
N(1)
14(1)
13(1)
22(1)
0(1)
-3(1)
-3(1)
N(2)
11(1)
13(1)
14(1)
0
1(1)
0
N(3)
22(1)
19(1)
27(1)
2(1)
11(1)
-3(1)
N(4)
12(1)
11(1)
14(1)
0
1(1)
0
Cl(1)
22(1)
25(1)
18(1)
-8(1)
2(1)
2(1)
Cl(2)
19(1)
14(1)
21(1)
5(1)
-4(1)
-1(1)
Cl(3)
25(1)
21(1)
13(1)
0
-1(1)
0
Cl(4)
11(1)
31(1)
18(1)
0
1(1)
0
Cl(5)
20(1)
24(1)
25(1)
-4(1)
-4(1)
-7(1)
Cl(6)
23(1)
19(1)
22(1)
6(1)
2(1)
6(1)
Cl(7)
21(1)
53(1)
13(1)
0
1(1)
0
Cl(8)
12(1)
59(1)
23(1)
0
-1(1)
0
69
Adduct: PCl2N]3.GaCl3
70
Asymmetric Unit: [PCl2N]3.GaCl3
71
Table 9. Crystal data and structure refinement for [PCl2N]3.GaCl3.
Empirical formula
Cl9 Ga N3 P3
Formula weight
523.71
Temperature
100(2) K
Wavelength
0.71073 Å
Crystal system
Monoclinic
Space group
P2(1)/c
Unit cell dimensions
a = 11.776(3) Å
= 90°
b = 10.830(3) Å
= 92.011(4)°
c = 23.865(6) Å
= 90°
Volume
3041.6(12) Å3
Z
7
Density (calculated)
2.001 Mg/m3
Absorption coefficient
3.220 mm-1
F (000)
1750
Crystal size
0.11 x 0.08 x 0.07 mm3
Theta range for data collection
1.71 to 28.33°.
Index ranges
-15<=h<=15, -13<=k<=14, -31<=l<=31
Reflections collected
25603
Independent reflections
7155 [R (int) = 0.0719]
Completeness to theta = 28.33°
94.4 %
Absorption correction
Semi-empirical from equivalents
Max. and min. transmission
0.8060 and 0.7066
Refinement method
Full-matrix least-squares on F2
Data / restraints / parameters
7155 / 0 / 289
Goodness-of-fit on F2
0.963
Final R indices [I>2sigma(I)]
R1 = 0.0397, wR2 = 0.0751
R indices (all data)
R1 = 0.0722, wR2 = 0.0797
Largest diff. peak and hole
0.627 and -0.552 e.Å-3
72
Table 10. Atomic coordinates (x 104) and equivalent isotropic displacement
parameters (Å2x 103) for [PCl2N]3.GaCl3. U(eq) is defined as one third of the
trace of the orthogonalized Uij tensor.
_____________________________________________________________________________
x
y
z
U(eq)
_____________________________________________________________________________
Ga(1)
3402(1)
6117(1)
1182(1)
15(1)
Ga(2)
10959(1)
740(1)
1310(1)
17(1)
Cl(1)
12003(1)
669(1)
589(1)
25(1)
Cl(2)
9626(1)
-611(1)
1308(1)
29(1)
Cl(3)
12011(1)
777(1)
2062(1)
27(1)
Cl(4)
11121(1)
3787(1)
371(1)
26(1)
Cl(5)
9345(1)
1685(1)
141(1)
24(1)
Cl(6)
11182(1)
3882(1)
2161(1)
28(1)
Cl(7)
9367(1)
1882(1)
2415(1)
25(1)
Cl(8)
6641(1)
4550(1)
1205(1)
32(1)
Cl(9)
8625(1)
6422(1)
1194(1)
29(1)
Cl(10)
6946(1)
10876(1)
1349(1)
26(1)
Cl(11)
4571(1)
12124(1)
1289(1)
22(1)
Cl(12)
3481(1)
8015(1)
2357(1)
22(1)
Cl(13)
6018(1)
7392(1)
2151(1)
24(1)
Cl(14)
6064(1)
7524(1)
365(1)
22(1)
Cl(15)
3531(1)
8153(1)
78(1)
19(1)
Cl(16)
1677(1)
6743(1)
1177(1)
23(1)
Cl(17)
3899(1)
5035(1)
1905(1)
24(1)
Cl(18)
3865(1)
5125(1)
445(1)
23(1)
P(1)
4737(1)
8415(1)
653(1)
14(1)
P(2)
4703(1)
8331(1)
1837(1)
16(1)
P(3)
5291(1)
10485(1)
1289(1)
16(1)
P(4)
9744(1)
3019(1)
669(1)
17(1)
P(5)
9774(1)
3112(1)
1852(1)
18(1)
P(6)
8316(1)
4625(1)
1218(1)
20(1)
N(1)
5019(3)
9823(3)
712(1)
17(1)
N(2)
4331(3)
7715(3)
1225(1)
15(1)
N(3)
4961(3)
9749(3)
1827(1)
18(1)
73
Table 10. Atomic coordinates (x 104) and equivalent isotropic displacement
parameters (Å2x 103) for [PCl2N]3.GaCl3. U(eq) is defined as one third of the
trace of the orthogonalized Uij tensor (continued).
N(4)
10093(3)
2372(3)
1275(1)
15(1)
N(5)
8796(3)
4082(4)
1794(2)
30(1)
N(6)
8750(3)
3976(3)
679(2)
22(1)
74
Table 11. Bond lengths [Å] and angles [°] for [PCl2N]3.GaCl3.
_____________________________________________________
Ga(1)-N(2)
2.048(3)
Ga(1)-Cl(16)
2.1410(12)
Ga(1)-Cl(18)
2.1473(12)
Ga(1)-Cl(17)
2.1514(12)
Ga(2)-N(4)
2.040(3)
Ga(2)-Cl(3)
2.1446(13)
Ga(2)-Cl(2)
2.1466(13)
Ga(2)-Cl(1)
2.1517(13)
Cl(4)-P(4)
1.9774(16)
Cl(5)-P(4)
1.9642(16)
Cl(6)-P(5)
1.9757(17)
Cl(7)-P(5)
1.9637(16)
Cl(8)-P(6)
1.9730(17)
Cl(9)-P(6)
1.9810(17)
Cl(10)-P(3)
1.9952(16)
Cl(11)-P(3)
1.9671(16)
Cl(12)-P(2)
1.9616(16)
Cl(13)-P(2)
1.9787(16)
Cl(14)-P(1)
1.9796(15)
Cl(15)-P(1)
1.9603(15)
P(1)-N(1)
1.567(4)
P(1)-N(2)
1.648(3)
P(2)-N(3)
1.566(4)
P(2)-N(2)
1.650(3)
P(3)-N(3)
1.572(4)
P(3)-N(1)
1.576(3)
P(4)-N(6)
1.563(4)
P(4)-N(4)
1.646(3)
P(5)-N(5)
1.561(4)
P(5)-N(4)
1.649(3)
P(6)-N(6)
1.569(4)
P(6)-N(5)
1.580(4)
N(2)-Ga(1)-Cl(16)
103.77(10)
75
Table 11. Bond lengths [Å] and angles [°] for [PCl2N]3.GaCl3 (continued)
N(2)-Ga(1)-Cl(18)
108.32(10)
Cl(16)-Ga(1)-Cl(18)
114.93(5)
N(2)-Ga(1)-Cl(17)
106.83(10)
Cl(16)-Ga(1)-Cl(17)
114.08(5)
Cl(18)-Ga(1)-Cl(17)
108.38(5)
N(4)-Ga(2)-Cl(3)
106.95(10)
N(4)-Ga(2)-Cl(2)
103.05(10)
Cl(3)-Ga(2)-Cl(2)
114.53(5)
N(4)-Ga(2)-Cl(1)
107.25(10)
Cl(3)-Ga(2)-Cl(1)
109.97(5)
Cl(2)-Ga(2)-Cl(1)
114.33(5)
N(1)-P(1)-N(2)
116.13(18)
N(1)-P(1)-Cl(15)
110.45(14)
N(2)-P(1)-Cl(15)
106.86(13)
N(1)-P(1)-Cl(14)
109.76(14)
N(2)-P(1)-Cl(14)
108.59(14)
Cl(15)-P(1)-Cl(14)
104.37(7)
N(3)-P(2)-N(2)
115.42(18)
N(3)-P(2)-Cl(12)
109.10(14)
N(2)-P(2)-Cl(12)
108.12(13)
N(3)-P(2)-Cl(13)
111.07(14)
N(2)-P(2)-Cl(13)
107.91(13)
Cl(12)-P(2)-Cl(13)
104.63(7)
N(3)-P(3)-N(1)
115.84(19)
N(3)-P(3)-Cl(11)
109.82(14)
N(1)-P(3)-Cl(11)
109.62(14)
N(3)-P(3)-Cl(10)
108.54(14)
N(1)-P(3)-Cl(10)
109.06(15)
Cl(11)-P(3)-Cl(10)
103.21(7)
N(6)-P(4)-N(4)
115.74(19)
N(6)-P(4)-Cl(5)
109.55(15)
N(4)-P(4)-Cl(5)
107.31(13)
N(6)-P(4)-Cl(4)
110.47(15)
76
Table 11. Bond lengths [Å] and angles [°] for [PCl2N]3.GaCl3 (continued)
N(4)-P(4)-Cl(4)
108.19(13)
Cl(5)-P(4)-Cl(4)
105.00(7)
N(5)-P(5)-N(4)
116.20(19)
N(5)-P(5)-Cl(7)
108.72(17)
N(4)-P(5)-Cl(7)
108.06(13)
N(5)-P(5)-Cl(6)
110.85(17)
N(4)-P(5)-Cl(6)
107.70(13)
Cl(7)-P(5)-Cl(6)
104.66(7)
N(6)-P(6)-N(5)
115.42(19)
N(6)-P(6)-Cl(8)
108.86(15)
N(5)-P(6)-Cl(8)
109.03(16)
N(6)-P(6)-Cl(9)
110.48(15)
N(5)-P(6)-Cl(9)
109.30(17)
Cl(8)-P(6)-Cl(9)
103.00(7)
P(1)-N(1)-P(3)
123.8(2)
P(1)-N(2)-P(2)
118.2(2)
P(1)-N(2)-Ga(1)
121.08(18)
P(2)-N(2)-Ga(1)
120.76(18)
P(2)-N(3)-P(3)
124.3(2)
P(4)-N(4)-P(5)
118.0(2)
P(4)-N(4)-Ga(2)
120.97(18)
P(5)-N(4)-Ga(2)
121.00(18)
P(5)-N(5)-P(6)
124.7(2)
P(4)-N(6)-P(6)
125.1(2)
_____________________________________________________________
Symmetry transformations used to generate equivalent atoms:
77
Table 12. Anisotropic displacement parameters (Å2x 103) for [PCl2N]3.GaCl3. The
anisotropic displacement factor exponent takes the form: -2 2[ h2 a*2U11 + ...
+ 2 h k a* b* U12
____________________________________________________________________________
U11
U22
U33
U23
U13
U12
_____________________________________________________________________________
Ga(1)
16(1)
15(1)
16(1)
1(1)
1(1)
0(1)
Ga(2)
16(1)
14(1)
22(1)
-1(1)
1(1)
2(1)
Cl(1)
19(1)
27(1)
28(1)
-8(1)
6(1)
2(1)
Cl(2)
24(1)
17(1)
45(1)
-4(1)
5(1)
-4(1)
Cl(3)
26(1)
29(1)
26(1)
4(1)
-6(1)
7(1)
Cl(4)
30(1)
26(1)
23(1)
2(1)
8(1)
-8(1)
Cl(5)
24(1)
26(1)
21(1)
-8(1)
-5(1)
2(1)
Cl(6)
37(1)
22(1)
26(1)
-5(1)
-4(1)
-7(1)
Cl(7)
28(1)
27(1)
20(1)
6(1)
7(1)
2(1)
Cl(8)
20(1)
23(1)
54(1)
6(1)
7(1)
1(1)
Cl(9)
25(1)
17(1)
46(1)
-1(1)
2(1)
0(1)
Cl(10)
17(1)
31(1)
30(1)
0(1)
-2(1)
-3(1)
Cl(11)
25(1)
14(1)
28(1)
-3(1)
1(1)
1(1)
Cl(12)
25(1)
23(1)
17(1)
2(1)
7(1)
1(1)
Cl(13)
24(1)
25(1)
21(1)
-2(1)
-5(1)
5(1)
Cl(14)
18(1)
24(1)
25(1)
0(1)
7(1)
3(1)
Cl(15)
19(1)
21(1)
15(1)
1(1)
-3(1)
-3(1)
Cl(16)
17(1)
27(1)
24(1)
1(1)
2(1)
1(1)
Cl(17)
29(1)
20(1)
24(1)
8(1)
-4(1)
-1(1)
Cl(18)
26(1)
19(1)
25(1)
-7(1)
7(1)
-2(1)
P(1)
16(1)
14(1)
13(1)
0(1)
1(1)
0(1)
P(2)
19(1)
16(1)
13(1)
0(1)
1(1)
1(1)
P(3)
18(1)
15(1)
16(1)
0(1)
0(1)
-1(1)
P(4)
19(1)
17(1)
14(1)
0(1)
0(1)
1(1)
P(5)
24(1)
16(1)
15(1)
-1(1)
2(1)
4(1)
P(6)
21(1)
16(1)
22(1)
3(1)
4(1)
5(1)
N(1)
23(2)
16(2)
13(2)
-1(2)
1(2)
-1(2)
N(2)
19(2)
15(2)
12(2)
2(2)
1(2)
-3(2)
N(3)
28(2)
13(2)
14(2)
0(2)
-2(2)
-4(2)
78
Table 12. Anisotropic displacement parameters (Å2x 103) for [PCl2N]3 GaCl3. The anisotropic
.
displacement factor exponent takes the form: -2 2[ h2 a*2U11 + ... + 2 h k a* b* U12
(continued)
N(4)
18(2)
12(2)
14(2)
0(2)
1(2)
2(2)
N(5)
38(3)
35(3)
18(2)
-4(2)
1(2)
22(2)
N(6)
30(2)
21(2)
15(2)
3(2)
0(2)
12(2)
______________________________________________________________________________
79