Synthesis and structures of bis(iminophosphorano)methanide chelate complexes with zinc and group 13

Article abstract of DOI:10.1016/j.poly.2018.11.056

The organolithium bis(iminophosphorano)methandiide dimer [Li₂C(Ph₂P[dbnd]NSiMe₃)₂]₂ ([Li₂-1]₂) reacts with 4 equiv of AlCl₃ in THF to generate the novel bimetallic alu

Full text of DOI:10.1016/j.poly.2018.11.056

Accepted Manuscript
Synthesis and Structures of Bis(iminophosphorano)methanide Chelate Com-
plexes with Zinc and Group 13
Jin Zhang, Sai Ge, Jianguo Zhao, Imran Ulhaq, Micheal J. Ferguson, Robert
McDonald, Guibin Ma, Cavell G. Ronald
PII:
S0277-5387(18)30781-2
https://doi.org/10.1016/j.poly.2018.11.056
POLY 13603
DOI:
Reference:
Polyhedron
To appear in:
Received Date:
Accepted Date:
26 September 2018
26 November 2018
Please cite this article as: J. Zhang, S. Ge, J. Zhao, I. Ulhaq, M.J. Ferguson, R. McDonald, G. Ma, C.G. Ronald,
Synthesis and Structures of Bis(iminophosphorano)methanide Chelate Complexes with Zinc and Group 13,
Polyhedron (2018), doi: https://doi.org/10.1016/j.poly.2018.11.056
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers
we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting proof before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

Synthesis and Structures of Bis(iminophosphorano)methanide Chelate
Complexes with Zinc and Group 13
Jin Zhang1, Sai Ge1, Jianguo Zhao1*, Imran Ulhaq2, Micheal J. Ferguson2, Robert
McDonald2, Guibin Ma1,2* and Cavell G Ronald2
1Institute of Carbon Materials Science, Shanxi Datong University, Datong, Shanxi
Province, 037009, PR China
2Chemistry Department, University of Alberta, Edmonton, Alberta, T6G 2G2, Canada
*Corresponding Author’s E-mail address: jgzhaoshi@163.com (Prof. J. Zhao) or
guibin@ualberta.ca (Dr. G. Ma)
Abstract:
The
organolithium
bis(iminophosphorano)methandiide
dimer
[Li2C(Ph2P=NSiMe3)2]2 ([Li2-1]2) reacts with 4 equiv of AlCl3 in THF to generate the
novel bimetallic aluminum carbene complex of [Li(THF)4][{C(Ph2P=NSiMe3)2}Al2Cl5]
(1). In addition, several new bis(iminophosphorano)methanide chelate-coordinated
complexes of [{CH(Ph2P=NSiMe3)2}AlCl2] (2), [{CH(Ph2P=NSiMe3)2}GaBr2] (3),
[{CH(Ph2P=NSiMe3)2}InCl2] (4), and [{CH(Ph2P=NSiMe3)2}InBr2] (5) are synthesized
in situ while organolithium bis(iminophosphorano)methandiide ([Li2-1]2) reacts with 2
equiv of metal halides AlCl3, GaBr3 InCl3 and InBr3 respectively in THF. Furthermore,
an unexpected complex of [{CH2(Ph2P=NSiMe3)2}ZnCl2] (6) is formed as [Li2-1]2 dimer
reacted with 2 equiv of ZnCl2 in situ. All six synthesized complexes (1, 2, 3, 4, 5 and 6)
in situ were isolated in solid and were structurally characterized by X-ray diffraction.
Complexes containing particular carbene to metal or ionic linking interaction bonds (1, 2,
3 and 4) were selected and further characterized in detail by DFT calculations using
Gaussian03 program. The DFT calculation demonstrates the existence of a carbene-Al σ
bond in structure 1 and ionic linkage interaction in structures 2-4.
Keywords: bis(iminophosphorano)methandiide dimer, organolithium, aluminum,
gallium, indium, zinc, DFT calculation.
1

Introduction
Metal complexes with chelate ligands have continued to attract scientific attention and
generated a considerable amount of interest in chemicals as well as catalytic applications
[1]. We [2] and others [3] have developed a chelate N,N-bidentate monoanionic of
bis(diphenyliminophosphorano)methanide
(LiHL)
or
bianionic
bis(diphenyliminophosphorano) methandiide (Li2L) ligand systems several years ago
through either single or double deprotonation of bis(diphenyliminophosphorano)methane
with lithium methide (Scheme 1).
Scheme 1
It was demonstrated that our ligand systems have abundant chemical bonding properties
and reactivities with transition metals, lanthanide and actinide metals, as well as main
group elements. E.g. formation complexes containing either single (C−M) or double
(C=M) carbene−metal bonds, or formation of monomeric and
bimetallic complexes, which showed great catalytic activities (Scheme 1)[4]. We
have learned from our synthesis experiments that the reactivities of these ligand systems,
especially dilithium Li2L salt, are pretty much dependent on the structures of metal
2

precursors. In addition, the metal properties and electronic configurations are critical
factors for how well the carbene will bind to the metal, through formation of either a
single or double bond between the carbene carbon and metal center. Compared to
transition and lanthanide metals, the chemistry of these chelate ligands with main group
elements have not been extensively explored. A few examples of Al3+ and Tl+ metals
were conducted in our laboratory so far [5], showing unusual reactivities and catalytic
activities, especially for Al complexes [6]. To further understand the reactivities of this
type of ligands with structural examples, especially with rarely studied closed shell main
group elements, we have extended our ligand system to main group 13 elements and a
few
bis(diphenyliminophosphorano)methandiide,
bis(diphenyliminophosphorano)methanide and bis(diphenyliminophosphorano)methane
chelate coordinated Al3+, Ga3+, In3+ and Zn2+ complexes. Complexes containing a six-
member-ring in boat conformation were prepared, isolated and structurally characterized
by X-ray diffraction and DFT calculations.
Experimental Section
General Considerations. All manipulations were performed either in an Ar-filled glove
box or under an Ar or N2 atmosphere using standard Schlenk techniques. Solvents were
dried over appropriate drying agents and degassed by three freeze-pump-thaw cycles
prior to use. The organolithium compounds [Li2-1]2 was prepared according to our
published procedures [2]. NMR spectra were recorded at ambient temperature using
THF-d8 or toluene-d8 solutions of the complexes on a Varian i400 spectrometer (161.9
13
MHz for 31P, 100.6 MHz for C) and referenced to residual solvent proton (1H), solvent
(13C), external 85% H3PO4 (31P). Elemental analyses were carried out at Analytical and
Instrumentation Laboratory, Department of Chemistry, University of Alberta.
Synthesis of [{C(Ph2P=NSiMe3)2}Al2Cl5][Li(C4H8O)4] (1)
To THF solution (10 ml) of [Li2-1]2 (0.115 g, 0.10 mmol) was added AlCl3 (0.054 g,
0.40 mmol) as a solid in a single portion at room temperature. The resulting solution was
stirred at room temperature overnight, during which the mixture turned into a clear light
yellow solution. The filtered THF solution was evaporated on a dynamic vacuum line and
the remaining powder was dissolved in 5 ml ether. The undissolved solid of LiCl was
3

removed by centrifugation. The yellow-green solution was evaporated under vacuum to
half of the volume and a few drops of dry toluene was added. The solution was kept
inside the freezer (-20° C) for a few days, during which white crystals formed. The top
liquid was taken and dried under vacuum. The product of 1 was obtained (0.124 g, yield
57.2%). Anal. Calcd for C47H70Al2Cl5LiN2O4P2Si2: C, 52.11; H, 6.51; N, 2.59. Found: C,
1
1
52.0; H, 6.67; N, 2.61. H NMR: H NMR(THF-d8): δ 7.94 (t, phenyl, 8H), 7.69 (d,
13
31
phenyl, 4H), 7.35 (t, phenyl, 8H), −0.24 (s, -Si(CH3)3, 18H). C{1H, P} NMR (THF-
d8): δ 135.71(s, phenyl), 133.68(s, phenyl), 132.22(s, phenyl), 128.18(s, phenyl), 3.31 (s,
Si(CH3)3). 31P{1H} NMR(THF-d8): δ 35.98 (s).
Synthesis of [{CH(Ph2P=NSiMe3)2}AlCl2] (2)
To THF solution (10 ml) of [Li2-1]2 (0.115 g, 0.10 mmol) was added AlCl3 (0.027 g,
0.20 mmol) as a solid in a single portion at room temperature. The isolation procedure
was similar as 1. The product of 2 was obtained (0.085 g, yield 65%). Anal. Calcd for
1
C31H39AlCl2N2P2Si2: C, 56.79; H, 6.00; N, 4.27. Found: C, 56.65; H, 6.03; N, 4.25. H
NMR(THF-d8): δ 7.82 (t, phenyl, 8H), 7.34 (d, phenyl, 4H), 7.10 (t, phenyl, 8H), −0.12
13
31
(s, -Si(CH3)3, 18H). C{1H, P} NMR (THF-d8): δ 132.7(s, phenyl), 131.3(s, phenyl),
31
129.7(s, phenyl), 127.0(s, phenyl), 3.82 (s, Si(CH3)3). P{1H} NMR(THF-d8): δ 29.88
(s).
Synthesis of [{CH(Ph2P=NSiMe3)2}GaBr2] (3)
To THF solution (10 ml) of [Li2-1]2 (0.115 g, 0.10 mmol) was added GaBr3 (0.062 g,
0.20 mmol) as a solid in a single portion at room temperature. The isolation procedure
was similar as 1. The product of 3 was obtained (0.118 g, yield 75%). Anal. Calcd for
1
C31H39Br2GaN2P2Si2: C, 47.29; H, 4.99; N, 3.56. Found: C, 47.50; H, 5.01; N, 3.53. H
NMR(THF-d8): δ 7.70 (t, phenyl, 8H), 7.34 (d, phenyl, 4H), 7.30 (t, phenyl, 8H), −0.13
(s, -Si(CH3)3, 18H). 13C{1H, 31P} NMR (THF-d8): δ 137.05(s, phenyl), 134.51(s, phenyl),
129.65(s, phenyl), 3.56 (s, Si(CH3)3). 31P{1H} NMR(THF-d8): δ 31.68 (s).
Synthesis of [{CH(Ph2P=NSiMe3)2}InCl2] (4)
4

To THF solution (10 ml) of [Li2-1]2 (0.115 g, 0.10 mmol) was added InCl3 (0.044 g,
0.20 mmol) as a solid in a single portion at room temperature. The isolation procedure
was similar as 1. The product of 4 was obtained (0.116 g, yield 79%). Anal. Calcd for
1
C31H39Cl2N2P2Si2In: C, 50.08; H, 5.29; N, 3.77. Found: C, 50.31; H, 5.27; N, 3.88. H
1
NMR: H NMR(THF-d8): δ 7.62 (t, phenyl, 8H), 7.36 (d, phenyl, 4H), 7.25 (t, phenyl,
8H), −0.03 (s, -Si(CH3)3, 18H). 13C{1H, 31P} NMR (THF-d8): δ 132.29(s, phenyl),
131.35(s, phenyl), 128.32 (s, phenyl), 3.47 (s, Si(CH3)3). 31P{1H} NMR(THF-d8): δ 33.2
(s).
Synthesis of [{CH(Ph2P=NSiMe3)2}InBr2] (5)
To THF solution (10 ml) of [Li2-1]2 (0.115 g, 0.10 mmol) was added InBr3 (0.071 g,
0.20 mmol) as a solid in a single portion at room temperature. The isolation procedure
was similar as 1. The product of 5 was obtained (0.123 g, yield 74%). Anal. Calcd for
1
C31H39Br2InN2P2Si2: C, 44.73; H, 4.72; N, 3.37. Found: C, 44.68; H, 4.64; N, 3.32. H
NMR (CDCl3): δ 7.60 (t, phenyl, 8H), 7.36 (d, phenyl, 4H), 7.26 (t, phenyl, 8H), −0.02
(s, -Si(CH3)3, 18H). 13C{1H, 31P} NMR (CDCl3): δ 133.89(s, phenyl), 132.51(s, phenyl),
31
131.22(s, phenyl), 128.24(s, phenyl), 3.62 (s, Si(CH3)3). P{1H} NMR(CDCl3): δ 32.92
(s).
Synthesis of [{CH2(Ph2P=NSiMe3)2}ZnCl2] (6)
To THF solution (10 ml) of [Li2-1]2 (0.115 g, 0.10 mmol) was added ZnCl2 (0.028 g,
0.20 mmol) as a solid in a single portion at room temperature. The isolation procedure
was similar as 1. The product of 6 was obtained (0.112 g, yield 80%). Anal. Calcd for
1
C31H40Cl2N2P2Si2Zn: C, 53.57; H, 5.80; N, 4.03. Found: C, 53.84; H, 5.78; N, 4.05. H
1
NMR: H NMR(THF-d8): δ 7.48 (q, phenyl, 8H), 7.32 (t, phenyl, 4H), 7.22 (t, phenyl,
8H), −0.094 (s, -Si(CH3)3, 18H). 13C{1H, 31P} NMR (THF-d8): δ 137.51(s, phenyl),
131.36(s, phenyl), 129.71(s, phenyl), 127.45(s, phenyl), 3.25 (s, Si(CH3)3). 31P{1H}
NMR(THF-d8): δ 30.78 (s).
Crystal Structure Determination. Suitable crystals of 1 to 6 were mounted on glass
fibers by means of mineral oil, and data were collected using graphite-monochromated
5

MoKα radiation (0.71073 Å) on a Bruker PLATFORM/ SMART 1000 CCD
diffractometer. The structure was solved by direct methods using SHELXL-90 [11a], and
refined using full-matrix least-squares on F2 (SHELXL-93) [11b]. All non-hydrogen
atoms in the structure compound were refined with anisotropic displacement parameters.
Selected crystal data and structure refinement details for 1-6 are listed in Table 1.
Computational Details. The geometric optimization and energy calculations were
performed with the Gaussian03 program [10a] based on the density functional theory
(DFT) method. The Becke's three-parameter hybrid functional with the Lee-Yang-Parr
correlation functional (B3LYP) [12] was employed for all calculations. For geometric
optimization, the LANL2DZ basis sets for Ga, In and 6-31G(d) for others. Once an
optimized geometry was obtained, imaginary frequencies were checked at the same level
by vibration analysis to verify the genuine minimum on the potential energy surface
(PES) and to evaluate the zero-point energy (ZPE) correction. The DFT wave functions
obtained at optimized structures were confirmed to be stable. Gaussian NBO analysis was
carried out for the final optimized structures [10b].
Results and Discussion
Synthesis and Crystal Structures
Transmetalation of the lithium methandiide complex, [Li2C(Ph2P=NSiMe3)2]2
([Li2L]2), with AlCl3 in a 1:4 molar ratio in THF followed by extraction with ether and
crystallization from ether/toluene afforded the corresponding aluminum complex
[Li(THF)4][{C(Ph2P=NSiMe3)2}Al2Cl5] (1) as colorless crystals in good yield (Scheme
2). Complex of [{CH(Ph2P=NSiMe3)2}AlCl2] (2) was isolated as crystalline solid from
the reactant solution of [Li2L]2 with AlCl3 salts in 1:2 molar ratio in THF. This compound
was prepared by reaction of [LiHC(Ph2P=NSiMe3)2] with AlCl3 in benzene [4s]. In a
similar
procedure,
the
bis(iminophosphorano)methanide
complexes
of
[{CH(Ph2P=NSiMe3)2}GaBr2]
(3), [{CH(Ph2P=NSiMe3)2}InCl2]
(4),
[{CH(Ph2P=NSiMe3)2}InBr2] (5) and [{CH2(Ph2P=NSiMe3)2}ZnCl2] (6) were
synthesized by reaction of [Li2L]2 with the corresponding metal halides in situ and
isolated in solid (Scheme 3).
6

Scheme 2
Scheme 3
The solid structure of 1 was investigated by single-crystal X-ray diffraction (Figure
1). Compound 1 is a bimetallic organometallic carbene compound and crystallizes in the
triclinic space group Pī, with two molecules in the unit cell. The selected bond lengths
and angles are given in Table 2. Two nitrogen atoms coordinate to Al(1) and generates
the heteroatomic six-member ring (-Al(1)-N(1)-P(1)-C(1)-N(2)-P(2)-). Four atoms of
P(1)-N(1)-N(2)-P(2) sit in a perfect plane, while Al(1) and C(1) are located above this
plane to form a boat conformation. At the front of the boat, two chelate nitrogen atoms
(N(1) and N(2)), and two chlorine atoms (Cl(1) and Cl(2)) coordinate to Al(1). At the tail
of the boat, PCP carbene center coordinates to Al(2) with three chlorine atoms (Cl(3),
7

Cl(4) and Cl(5)). Both aluminum centers (Al(1) and Al(2)) adapt to a slightly twisted
tetrahedral geometry as expected. In addition, four atoms of carbene and its bonded three
atoms (P(1), P(2) and Al(2)) are almost within one plane as well. The bond length of
carbene-Al (Al(2)-C(1) = 1.966(4) Å) is shorter than the NHC heterocyclic carbene
aluminum structure (Al-C = 2.009(5)) [7], which has the same coordination environment
as 1 (C AlCl3). The bond lengths of Al-C (Al(2)-C(1) = 1.966(4) Å), Al-N (Al(1)-N(1)
=1.866(3), and Al(1)-N(2) = 1.871(3) Å) in 1 are notably shorter in comparison with our
previously determined carbon bridged two aluminum compound [5b]
[(Me2Al)2C(Ph2P=NSiMe3)2]2 (average Al-N = 1.930(3) Å) and Al-C = 2.119(3) Å),
which indicates a strong bonding interaction in 1.
Scheme 4
One
aluminum
bis(diphenyliminophosphorano)methanide
compound
of
[{CH(Ph2P=NSiMe3)2}AlCl2] (2) was isolated and the crystal structure solved by X-ray
diffraction (Figure 2). The core structural conformation of 2 is compatible to 1 with
similar bond lengths (Scheme 4 and Table 2). Instead of carbene coordinated to AlCl3 as
shown in 1 with one protonated H in 2. The C(1)---Al distance of 2.763(3) Å is
considerably longer than the Al-C bonding lengths, indicating there is no direct bonding
interaction. However, it is notably shorter than the C(1)-Al(1) distance in 1 (C(1)-Al(1) =
2.957(3) Å), suggesting some ionic link interaction between positive charge (Al) and
negative charge (C(1)), which is supposed non-existent in the structure 1 between C(1)
and Al(1).
8

The crystal structures of 3 to 5 were all solved using X-ray diffraction (see Figure 3 to
Figure 5; selected bond lengths and angles in Table 2). To the best of our knowledge, the
crystal structures even with the preparation of indium metal compounds with this type
ligand have not been reported in literature. However, one structure of
[{CH(Ph2P=NSiMe3)2}GaCl2] was previously determined [4s] for the gallium metal. The
solid structure of 3 [{ 2-CH(Ph2P=NSiMe3)2}GaBr2] is in the same space group as that of
the previously reported chloride coordinated compound, with compatible Ga-N bond
lengths and N-Ga-N angle as well as the same boat conformation [4s]. The
pseudotetrahedral coordination sphere about Ga is defined by the two phosphinimine
nitrogen atoms and the two bromides. The “bite angle” of the bisphosphinimine anion is
113.88(14)°, while the Br(1)-Ga-Br(2) angle is 105.29(2)°. The distance between C(1)
with charge (-1) and Ga with charge (+1) (2.913(3) Å) is shorter than Al(1)-C(1) distance
in structure 1 (2.957(3) Å) regardless of the long Ga-N bonds in structure 3, which
indicates the existence of ionic link interaction within 3 as similarly presented in 2.
Structures of two indium compounds with chloride (4) and bromide (5) are similar to
each other, both having the same conformation as 2 and 3. Based on the atomic distances
between C(1) and In within the molecular structures (2.763(3) Å (4) and 2.803(3) Å (5)),
it clearly indicates the existence of ionic linkage interaction.
The crystal structure of zinc compound 6 is shown in Figure 6 and the selected bond
lengths and angles are listed in Table 2. The zinc coordination sphere as expected is
pseudotetrahedral with two nitrogen atoms and chlorides, but the structure is not identical
to 2-5, whereas the carbon is single protonated. The distance between C(1) and zinc
within the heterocyclic six-member ring, C(1)-Zn = 3.156(3) Å, is the longest compared
with structures 2-5, which points to a lack of ionic link interaction in 6. This is further
understood as 6 is neutral, and ionic linkage interaction can only exist when there is
positive/negative charge separation.
The structural features of the determined crystal structures are all analogous to
formation of the heterocyclic six-member ring (CP2N2M, M = Al, Ga, In and Zn) as boat
conformation. In contrast to the conformation of 1, the boat shape of 2 is more flat with
larger N(1)-Al-N(2) and P(1)-C(1)-P(2) angles and shorter distances of C(1) and Al
above the P2N2 plane (Table 2). This could be due to the C(1)—Al distance shrinkage
9

caused by attraction interaction between the negative charge around C(1) and positive
charge around Al. It is interesting to note that in analogous structures 2-5, the N(1)-M-
N(2) and P(1)-C(1)-P(2) bond angles are almost identical in compounds 2 and 3 for Al
and Ga, and in compounds 4 and 5 for In, no matter where chloride or bromide
coordinates to the metals. However, these two angles (N(1)-M-N(2) and P(1)-C(1)-P(2),
M = Zn) were the smallest (Table 2) in 6, which also had the longest C(1)-M (M = Zn)
atomic distance (3.156(3) Å) compared to structures (2-5, from 2.763(3) to 2.913(3) Å).
These differences between 2-5 and 6 indicate the existence of an attraction interaction
between separated positive and negative charges within molecules in 2-5, which could
cause shrinking of distance C(1)-M and eventually enlarge the two angles.
Both of the P-C(carbon) lengths in 1-5 are noticeably shorter than that found for
parent P-C(carbon) in H2-1 [8] (P(1)-C(1) = 1.708(2) ∼ 1.7289(3) vs 1.827(1) Å), while
the P-N distances are considerably longer (P(1)-N(1) and P(2)-N(2) = 1.6260(15) ∼
1.647(3) vs 1.539(2) Å). The electronically delocalized effect inside the heterocyclic 6-
membered ring introduces a structural bond length difference between H2-1 and bound 1-
5. This observation is similar to our previously studied complexes and consistent with our
suggestion of -electron delocalization discussed previously [4i, 4h, 4k, 4n, 4o, 9].
DFT Calculations
The interested bonding model molecules, [{C(Me2P=NSiH3)2}Al2Cl5]- (1a),
[{HC(Me2P=NSiH3)2}AlCl2]
(2a)
containing
Al-carbene
bond,
[{HC(Me2P=NSiH3)2}GaBr2] (3a) and [{HC(Me2P=NSiH3)2}InCl2] (4a) presenting ionic
linkage interactions, were selected and further characterized by Gaussian-03 DFT
calculations as well as NBO analysis for 1a [10]. The HOMO of four model structures is
shown in Figure 7, it is seen that 1a is obviously different than those of 2a-4a. Based on
the molecular orbital coefficients (MOCs), it can be explained that the bonding
interaction to metals of carbene (P2C) is different than its protonated (P2CH) carbon. 1a
to 4a all contain the σ bond between carbon and two P by overlapping their pz atomic
orbitals. In addition to the σ bond, 2a to 4a also have nonbonding free electron of py
atomic orbital around the carbon, making the surface of the molecular orbital electron
10

shell unsymmetric as shown in Figure 7. This finding is in agreement with the crystal
structures that show there is one remaining negative charge around the carbon center.
Unlike structures 2a-4a which are similar in bonding, 1a is a novel aluminum carbene
compound. The NBO analysis was performed on this novelty structure. After geometry
optimization calculation, the structural data show that two of P-C, P-N and N-Al bond
lengths are identical within the six-membered ring, while two Cl-Al bond lengths around
Al(1) are not equivalent (see SI). Two of the three Cl-Al bond lengths around Al(2) are
equivalent but not identical to the third one (See SI), which is in agreement with the
crystal structural data (1). NBO analysis shows around Al(2) metal that the carbene-Al
bond is 13.3% from the Al(2) s0.33p0.67 hybrid orbital and 86.7% from the carbene
s0.32p0.68 hybrid orbital, while the two Cl(4), Cl(5) to Al(2) is 86.4% Cl s0.37p0.63 and
13.6% Al(2) s0.23p0.77 hybrid orbitals respectively and Cl(3)-Al(2) is 86.1% from Cl
s0.36p0.64 and 13.9% from Al(2) s0.24p0.76 as well. For Al(1) metal center, N-Al is 8.3%
from Al s0.29p0.71 and 91.7% from N s0.33p0.67 hybrid orbital, and Cl(1)-Al(1) is 13.7% Al
s0.24 p0.76 and 86.3% Cl s0.36p0.64 as well as Cl(2)-Al(1) is 13.5% Al s0.22p0.78 and 86.5% Cl
s0.38p0.62 hybrid orbitals as shown in Figure 8 (details listed in SI).
Conclusions
The reactions of bis(diphenyliminophosphorano) methandiide (Li2L) ligand with
group 13 metals are conducted, and one stable air-sensitive carbene aluminum compound
(1) was isolated and characterized by crystallography. Several novel unexpected
complexes resulted as the final products of Ga and In metals. No carbene-metal bond
formed after reaction with this bianionic electron rich ligand in situ, and eventually one
protonated carbon coordinated compounds (2, 3, 4 and 5) was isolated in solid. This
indicates that carbene bound Ga and In are not stable enough to hinder its protonated
trend. As we know, the second proton of P-CH--P is more strongly bonded than the first
proton in P-CHH-P, and the bianionic ligand (P-C2-P) tends to back to P-CH-P while it is
not strongly bound by a metal center, which is the case for Ga and In metals. As for Zn,
both in reactions of H2L with Zn(CH3)2 previously [4u] or Li2L with ZnCl2 herein, no
species with carbene metal bond formation was generated. This study clearly
demonstrates that the d orbital-filled main group 13 elements have different metal-
11

bonding behavior than those of the transition metals lanthanides and actinides, while
reacting with the electron rich PCP carbene ligand. In comparing the distance between
C(1) and metal ions within the heterocyclic six-member ring of 1 and 6 to 2-5, we have
determined the existence of an ionic linkage or separation positive/negative charge
attraction interaction in 2-5.
Acknowledgement. We are grateful to Shanxi ‘1331 Project’ Foundation for the
Construction of Collaborative Innovation Center of Graphene Industrial Application. We
also want to thank the Natural Sciences and Engineering Research Council (NSERC) of
Canada for financial support of this work in terms of a Discovery Grant. The authors
would like to thank the University of Alberta for support to maintain the X-Ray
Crystallography, and Analytical and Instrumentation laboratories at the Department of
Chemistry which were essential for this work.
Supporting Information Available: Crystallographic data (as CIF files) 1-6, the
different views of the structures (Figures S1-1 to S1-6) and selected bond
distances and bond angles (Table S1-1 to S1-6) and some Gaussian
calculation and NBO analysis data.
References:
[1] See for example: (a) S. W. Kohl, L. Weiner, L. Schwartsburd, L. Konstantinovski, L.
J. Shimon, Y. Ben-David, M. A. Iron, D. Milstein, Consecutive thermal H2 and light-
induced O2 evolution from water promoted by a metal complex, Science 324 (2009)
74-77 (DOI: 10.1126/science.1168600). (b) S. P. Green, C. Jones, A. Stasch, Stable
magnesium(I) compounds with Mg-Mg bonds, Science 318 (2007) 1754-1757 (DOI:
10.1126/science.1150856).
[2] (a) K. Aparna, R. P. Kamalesh Babu, R. McDonald, R. G. Cavell,
[Ph2P(NSiMe3)]2CLi2: A dilithium dianionic methanide salt with an unusual Li4C2
cluster structure, Angew. Chem. Int. Ed. 38 (1999) 1483-1484 (DOI:
10.1002/(SICI)1521-3773(19990517)38:10<1483::AID-ANIE1483>3.0.CO;2-D). (b)
M. Klobukowski, S. A. Decker, C. C. Lovallo, R. G. Cavell, Structure and bonding in
12

an octahedral Li4C2 cluster, the dilithium bis {dihydrido(silylimino)phosphorano}
methanide dimer. A combined DFT–AIM analysis, Theochem – J. Mol. Struct. 536
(2001) 189-194 (https://doi.org/10.1016/S0166-1280(00)00626-6).
[3]
C.
M.
Ong,
D.
W.
Stephan,
Lithiations
of
bis-diphenyl-N-
trimethylsilylphosphiniminomethane:ꢀ An X-ray structure of a 1,1-dilithiomethane
derivative, J. Am. Chem. Soc. 121(1999) 2939-2940 (DOI: 10.1021/ja9839421).
[4] See for example: Single C-M bond, (a) G. Aharonian, K. Feghali, S. Gambarotta, G.
P. A. Yap, Stability of trivalent vanadium alkyl and hydride supported by a chelating
phosphinimido
ligand,
Organometallics
20
(2001)
2616-2622
(DOI:
10.1021/om0101588). (b) S. T. Liddle, D. P. Mills, B. M. Gardner, J. McMaster, C.
Jones, W. D. Woodul, A heterobimetallic gallyl complex containing an unsupported
Ga−Y bond, Inorg. Chem. 48 (2009) 3520-3522 (DOI: 10.1021/ic900278t). (c) M. J.
Sarsfield, H. Steele, M. Helliwell, S. J. Teat, Uranyl bis-iminophosphorane complexes
with in- and out-of-plane equatorial coordination, Dalton Trans. (2003) 3443-3449
(DOI: 10.1039/B304602H). (d) G.-B. Ma, M. Ferguson, R. McDonald, R. G. Cavell,
Rare,
hexatomic,
boat-shaped,
cross-linked
bis(iminodiphenylphosphorano)methanediide pincer carbon bridged photoluminescent
copper clusters capped with methyl or halide bridges, Organometallics 29 (2010)
4251-4264 (DOI: 10.1021/om1002478). Double C=M bond: (e) S. T. Liddle, J.
McMaster, J. C. Green, P. L. Arnold, Synthesis and structural characterisation of an
yttrium–alkyl–alkylidene,
Chem.
Commun.
(2008)
1747-1749
(DOI:
10.1039/B719633D). (f) K. Aparna, M. Ferguson, R. G. Cavell, A monomeric
samarium bis(Iminophosphorano) chelate complex with a Sm=C bond, J. Am. Chem.
Soc. 122 (2000) 726-727 (DOI: 10.1021/ja9936114). (g) R. P. Kamalesh Babu, R.
McDonald, R. G. Cavell, Nucleophilic reactivity of the multiply bonded carbon center
in group 4 pincer bis(iminophosphorano)methanediide complexes, Organometallics 19
(2000) 3462-3465 (DOI: 10.1021/om000181d). (h) R. P. Kamalesh Babu, R.
McDonald, R. G. Cavell, The first hafnium methandiide complexes: the assembly of
an entire triad of group 4 metal ‘pincer’ bis(phosphinimine) complexes possessing the
M=C carbene–ylide structure, Chem. Commun. (2000) 481-482 (DOI:
10.1039/A909771F). (i) K. Aparna, R. P. Kamalesh Babu, R. McDonald, R. G. Cavell,
13

The first biscarbene complex of a group 4 metal: [Zr{C(Me2P=NSiMe3)2}2], Angew.
Chem. Int. Edit. 40 (2001) 4400-4402 (https://doi.org/10.1002/1521-
3773(20011203)40:23<4400::AID-ANIE4400>3.0.CO;2-W). (j) R. G. Cavell, R. P.
Kamalesh Babu, K. Aparna, R. McDonald, Novel metal−carbon multiply bonded
twelve-electron complexes of Ti and Zr supported by a bis(phosphoranimine) chelate,
J. Am. Chem. Soc. 121 (1999) 5805-5806 (DOI: 10.1021/ja984087o). (k) G.-B. Ma,
M. J. Ferguson, R. McDonald, R. G. Cavell, Actinide metals with multiple bonds to
carbon: synthesis, characterization, and reactivity of U(IV) and Th(IV)
bis(iminophosphorano)methandiide pincer carbene complexes, Inorg. Chem. 50
(2010) 6500-6508 (DOI: 10.1021/ic102537q). For example: Bimetallic: (l) K. Aparna,
R. McDonald, R. G. Cavell, Chromium bis(phosphoranimine) complexes; bridging
chromium carbenes with no CO or Cp supporting ligands, Chem. Commun. (1999) 1993-
1994 (DOI: 10.1039/A905241K). (m) M. Fang, N. D. Jones, R. Lukowski, J. Tjathas,
M. J. Ferguson, R. G. Cavell, A bimetallic, coordinated‐ketene complex formed from
a bimetallic lithium–carbon spirocycle by lithium‐mediated insertion of CO into a
rhodium–carbon bond, Angew. Chem. Int. Ed. 45 (2006) 3097-3101
(https://doi.org/10.1002/anie.200503814). (n) M. Fang, N. D. Jones, K. Friesen, G.-Y.
Lin, M. J. Ferguson, R. McDonald, R. Lukowski, R. G. Cavell, Bimetallic, spirocyclic,
methylene-bridged carbene complexes of rhodium and palladium derived by stepwise
metalations of lithiated bis(diphenylphosphoranotrimethylsilylimido)methandiide,
Organometallics, 28 (2009) 1652–1665 (DOI:10.1021/om8005678). (o) G.-B. Ma, R.
McDonald, R. G. Cavell,
A
spirocyclic, bimetallic, carbon-bridged
bis(iminophosphorano)methanediide complex of palladium(II): synthesis, crystal
structure, solution behavior, and DFT bonding analysis, Organometallics 29 (2010)
52-60 (DOI: 10.1021/om900571k). For example: chelate six-member ring: (p) T. K.
Panda, P. W. Roesky, P. Larsen, S. Zhang, C. Wickleder, Reactions of potassium
bis(phosphinimino)methanide with group 11 compounds, Inorg. Chem. 45 (2006)
7503-7508 (DOI: 10.1021/ic060932p). (q) M. Rastätter, A. Zulys, P. W. Roesky,
Bis(phosphinimino)methanide rare earth amides: synthesis, structure, and catalysis of
hydroamination/cyclization,
hydrosilylation,
and
sequential
14

hydroamination/hydrosilylation, Chem. Eur. J. 13 (2007) 3606-3616
(https://doi.org/10.1002/chem.200601510). (r) C. M. One, P. McKarns, D. W.
Stephan, Neutral and cationic group 13 phosphinimine and phosphinimide complexes,
Organometallics 18 (1999) 4197-4204 (DOI: 10.1021/om9904044). (s) M. T. Gamer,
S. Dehnen, P. W. Roesky, Synthesis and structure of yttrium and lanthanide
bis(phosphinimino)methanides, Organometallics
20 (2001) 4230-4236 (DOI:
10.1021/om0102955). (t) K. Aparna, R. McDonald, R. G. Cavell, Structure and
reactivity of a methyl zinc bis(iminophosphorano)methanide chelate complex,
Organometallics 18 (1999) 3775-3777 (DOI: 10.1021/om990415x). (u) R. P.
Kamalesh Babu, K. Aparna, R. McDonald, R. G. Cavell, Monomeric alkali metal (Li,
Na, K) complexes of bis(iminophosphorano)methanides, Organometallics 20 (2001)
1451-1455 (DOI: 10.1021/om000982g). (v) M. T. Gamer, P. W. Roesky, I. Palard, M.
L. Hellaye, S. M. Guillaume, In situ formation of bis(phosphinimino)methanide rare
earth alkoxide initiators for the ring-opening polymerization of ε-caprolactone,
Organometallics 26 (2007) 651-657 (DOI: 10.1021/om0608307). For example:
Reviews: (w) R. G. Cavell, R. P. Kamalesh Babu, K. Aparna, Early transition metal
and lanthanide bis(iminophosphorano)methandiide complexes; ‘pincer’ and bridging
bis(phosphorus) metal carbenes, J. Organomet. Chem. 617 (2001) 158-169 (refs.
therein) (https://doi.org/10.1016/S0022-328X(00)00735-X). (x) D. Morales-Morales,
C. M. Jensen, (Editors) The Chemistry of Pincer Compounds, R. G. Cavell, Chapter
14, Pincers, Chelate and Spirocyclic Metal Carbene Complexes from
Bis(iminophosphorano)methane Ligands, 2007, p: 311-346. Elsevier B. V.
[5] (a) K. Aparna, R. McDonald, R. G. Cavell, Carbon−carbon double bond formation
Reactions of the unique spirocyclic aluminum bis(iminophosphorano)methandiide
complex:ꢀ Insertion of heteroallenes into aluminum-carbon bonds, J. Am. Chem. Soc.
122 (2000) 9314-9315 (DOI: 10.1021/ja001445q). (b) K. Aparna, R. McDonald, M.
Ferguson, R. G. Cavell, Novel dialkyl aluminum bis(iminophosphorano)methanide
and methanediide complexes, Organometallics
18 (1999) 4241-4243 (DOI:
10.1021/om990486w). (c) G.-B. Ma, M. Ferguson, R. G. Cavell, A geminal dithallated
15

bis(iminodiphenylphosphorano)methine carbon bridged dimer bound by Tl–Tl
interactions, Chem Commun. 46 (2010) 5370-5372 (DOI: 10.1039/c0cc01088j).
[6] R. G. Cavell, K. Aparna, R. P. Kamalesh Babu, Q. Wang, Aluminum
bis(iminophosphorano)methanide and methandiide complexes—transition metal-free
ethylene polymerization cationic catalyst precursors, J. Mol. Catal. A, 189 (2002) 137-
143 (https://doi.org/10.1016/S1381-1169(02)00205-4).
[7] A. Stasch, S. Singh, H. W. Roesky, M. Noltemeyer, H. G. Schmidt, Adducts of
aluminum and gallium trichloride with a N‐heterocyclic carbene and an adduct of
aluminum trichloride with a thione, Eur. J. Inorg. Chem. (2004) 4052-4055 (DOI:
10.1002/ejic.200400247).
[8] A. Müller, M. Möhlen, B. Neumüller, N. Faza, W. Massa, K. Dehnicke, Crystal
structures
of
the
silylated
phosphaneimines
Me3SiNP(c-C6H11)3
and
(Me3SiNPPh2)2CH2, Z. Anorg. Allg. Chem. 625 (1999) 1748-1751.
[9] (a). R. P. Kamalesh Babu, R. McDonald, S. A. Decker, M. Klobukowski, R. G.
Cavell, New zirconium hydrocarbyl bis(phosphoranimino) “pincer” carbene
complexes, Organometallics 18 (1999) 4226-4229 (DOI: 10.1021/om9901473). (b) N.
D. Jones, G. Lin, R. A. Gossage, R. McDonald, R. G. Cavell, Synthesis, structure, and
reactivity of an unusual platinum olefin carbene complex, [(η4-
cod)Pt{=C(Ph2P=NSiMe3)2-κC,κN}], Organometallics 22 (2003) 2832-2841 (DOI:
10.1021/om030003v) [Erratum: Organometallics 22 (2003) 5378].
[10] (a) M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R.
Cheeseman, V. G. Zakrzewski, J. A. Montgomery Jr, R. E. Stratmann, J. C. Burant, S.
Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J.
Tomasi, V. Barone, M. Cossi, R. Cammi, B. Menucci, C. Pomelli, C. Adamo, S.
Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, N. Rega,
P. Salvador, J. J. Dannenberg, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B.
Foresman, J. Cioslowski, J. V. Ortiz, G. Baboul, B. B. Stefanov, G. Liu, A. Liashenko,
P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-
Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. G. Johnson,
W. Chen, M. W. Wong, J. L. Andres, C. Gonzalez, M. Head-Gordon, E. S. Replogle,
16

J. A. Pople, Revision C02 Gaussian, Inc., Pittsburgh PA, 2004. (b) E. D. Glendening,
A. E. Reed, J. E. Carpenter, F. Weinhold, NBO version 3.1.
[11] (a) G. M. Sheldrick, Phase annealing in SHELX-90: Direct methods for larger
structures,
Acta
Crystallogr.
A46
(1990)
467-473
(https://doi.org/10.1107/S0108767390000277). (b) G. M. Sheldrick, SHELXL-93.
Program for crystal structure determination. University of Göttingen, Germany, 1993.
[12] (a) A. D. Becke, Density‐functional thermochemistry. III. The role of exact
exchange, J. Chem. Phys. 98 (1993) 5648-5652 (https://doi.org/10.1063/1.464913). (b)
C. Lee, W. Yang, R. G. Parr, Development of the Colle-Salvetti correlation-energy
formula into a functional of the electron density, Phys. Rev. B 37 (1998) 785-789
(DOI: https://doi.org/10.1103/PhysRevB.37.785). (c) S. H. Vosko, L. Wilk, M. Nusair,
Accurate spin-dependent electron liquid correlation energies for local spin density
calculations:
a
critical analysis, Can. J. Phys. 58 (1980) 1200-
1211(https://doi.org/10.1139/p80-159).
17

Figure 1. Perspective view of the [{C(Ph2PNSiMe3)2}Al2Cl5]- anion showing the atom
labeling scheme. Non-hydrogen atoms are represented by Gaussian ellipsoids at the 20%
probability level. Hydrogen atoms are not shown.
18

Figure 2.
Perspective view of the [Cl2Al{κ2–HC(Ph2PNSiMe3)2}] molecule showing
the atom labelling scheme. Non-hydrogen atoms are represented by
Gaussian ellipsoids at the 20% probability level. The hydrogen atom
attached to C(1) is shown with an arbitrarily small thermal parameter; all
other hydrogens are not shown.
19

Figure 3.
Perspective view of the [Br2Ga{κ2–HC(Ph2PNSiMe3)2}] molecule
showing the atom labelling scheme. Non-hydrogen atoms are represented
by Gaussian ellipsoids at the 20% probability level. The hydrogen atom
attached to C(1) is shown with an arbitrarily small thermal parameter; all
other hydrogens are not shown.
20

Figure 4.
Perspective view of the [Cl2In{κ2–HC(Ph2PNSiMe3)2}] molecule showing
the atom labelling scheme. Non-hydrogen atoms are represented by
Gaussian ellipsoids at the 20% probability level. The hydrogen atom
attached to C(1) is shown with an arbitrarily small thermal parameter; all
other hydrogens are not shown.
21

Figure 5.
Perspective view of the [{CH(Ph2PNSiMe3)2}InBr2] molecule showing the
atom labelling scheme. Non-hydrogen atoms are represented by Gaussian
ellipsoids at the 20% probability level. Only the methine hydrogen atom is
shown (with arbitrarily small thermal parameter); all other hydrogen
atoms are not shown.
22

Figure 6. Perspective view of the [κ2–{CH2(Ph2P=NSiMe3)2}ZnCl2] molecule showing
the atom labelling scheme. Primed atoms are related to unprimed ones by the
crystallographic mirror plane located at (x, ¼, z). Non-hydrogen atoms are
represented by Gaussian ellipsoids at the 20% probability level.
23

Figure
7.
HOMO
of
[{C(Me2P=NSiH3)2}Al2Cl5]-
(1a)
(top,
left),
[{HC(Me2P=NSiH3)2}AlCl2] (2a) (top, right), [{HC(Me2P=NSiH3)2}GaBr2]
(3a) (bottom, left) and [{HC(Me2P=NSiH3)2}InCl2] (4a) (bottom, right).
24

Figure 8. NBO of Al-C (top, left), Al-Cl (top, middle) and Al-N (top, right) bonds of
[{C(Me2P=NSiH3)2}Al2Cl5]- (1a).
25

Table 1. Crystal data and structure refinement details for complexes 1-6
Empirical formula
C47H70Al2Cl5LiN2O4P2
Si2 2C7H8 (1)
C31H39Br2GaN2P2Si2 (3)
C31H39AlCl2N2P2Si2⋅2C4
H8O (2)
Formula weight
1267.59
799.85
787.30
Crystal system
Crystal Dimensions
Space group
Triclinic
0.48×0.41×0.27 mm
Pī(No. 2)
Triclinic
0.32×0.30×0.20 mm
Pī(No. 2)
Monoclinic
0.26×0.24×0.17 mm
P2 /c (No. 14)
1
Unit cell parameters
a (Å)
b (Å)
c (Å)
α (°)
12.933(2)
15.697(3)
17.787(3)
73.594(2)
80.332(2)
81.510(2)
3395.6(9)
2
11.7241(13)
12.1905(13)
17.3594(19)
101.6150(14)
100.4737(14)
113.8145(13)
2125.4(4)
2
12.1720(6)
20.8331(10)
15.0581(8)
β (°)
113.1782(6)
γ (°)
Volume (Å3)
3510.2(3)
4
Z
Calculated density (g cm-3)
Temperature, K
μ (MoKα), (mm-1)
θ range for data collection (°)
Index ranges
1.240
173.2(1)
0.366
1.250
173.2(1)
0.340
0.3 to 26.45
1.490
173.2(1)
3.243
0.3 to 27.54
0.3 to 26.36
-16 ≤ h ≤ 16
-20 ≤ k ≤ 20
-14 ≤ h ≤ 14
-15 ≤ k ≤ 15
-15 ≤ h ≤ 15
-26 ≤ k ≤ 26
-23 ≤ l ≤ 23
15360
9438
15360/80/624
1.026
-21 ≤ l ≤ 21
8688
6448
8688/10/467
1.057
-18 ≤ l ≤ 18
7159
5380
7159/0/361
1.047
Independent reflections
Observed reflections
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices
2
R1 = 0.0772
wR2 = 0.2647
R1 = 0.0455
wR2 = 0.1298
R1 = 0.0412
wR2 = 0.1177
-1.324 and 0.556 e/Å3
[F0 ≥ 2σ(F0)]
2
2
wR2 [F0 ≥ -3σ(F0 )]
Large difference peak and hole -0.905 and 1.085 e/Å3 -0.280 and 0.548 e/Å3
26

Empirical formula
Formula weight
C31H39Cl2InN2P2Si2
⋅2C4H8O (4)
887.69
C31H39Br2InN2P2Si2
(5)
832.40
C31H40Cl2N2P2Si2
C4H8O (6)
787.30
Crystal system
Crystal Dimensions
Space group
Triclinic
0.45×0.43×0.20 mm
Pī(No. 2)
Monoclinic
0.38×0.16×0.15 mm
Monoclinic
0.43×0.36×0.14 mm
P2 /c (No. 14)
P2 /m (No. 11)
1
1
Unit cell parameters
a (Å)
b (Å)
c (Å)
α (°)
11.9930(4)
12.1868(5)
17.7776(7)
103.1082(4)
102.6668(4)
113.5754(4)
2175.04(14)
2
12.3143(9)
20.8213(15)
15.2506(11)
9.1879(5)
20.1148(10)
10.7099(6)
β (°)
113.2510(10)
102.7190(10)
γ (°)
Volume (Å3)
3592.7(5)
4
1930.76(18)
2
Z
Calculated density (g cm-3)
Temperature, K
μ (MoKα), (mm-1)
θ range for data collection (°)
Index ranges
1.355
173.2(1)
0.829
0.3 to 27.48
1.539
173.2(1)
3.061
1.32
193.2(1)
0.949
0.3 to 27.51
0.3 to 27.00
-15 ≤ h ≤ 15
-15 ≤ k ≤ 15
-15 ≤ h ≤ 15
-27 ≤ k ≤ 26
-11 ≤ h ≤ 11
-26 ≤ k ≤ 26
-23 ≤ l ≤ 23
9854
9047
9854/0/451
1.048
-18 ≤ l ≤ 19
8224
6687
8224/0/361
1.025
-13 ≤ l ≤ 13
4541
4118
4541/0/187
1.076
Independent reflections
Observed reflections
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices
2
R1 = 0.0263
wR2 = 0.0695
R1 = 0.0266
wR2 = 0.0627
-2.82 and 0.507 e/Å3
R1 = 0.0259
wR2 = 0.0757
-0.248 and 0.492 e/Å3
[F0 ≥ 2σ(F0)]
2
2
wR2 [F0 ≥ -3σ(F0 )]
Large difference peak and hole -0.555 and 0.647 e/Å3
27

Table 2. Selected bond lengths (Å) and angles (°) for compounds 1-6
Compound 1
Al(1)-Cl(1)
Al(1)-Cl(2)
Al(1)-N(1)
Al(1)-N(2)
Al(2)-C(1)
Al(2)-Cl(3)
Al(2)-Cl(4)
Al(2)-Cl(5)
C(1)-P(1)
2.1460(19)
2.1684(15)
1.866(3)
N(1)-Al(1)-N(2)
P(1)-C(1)-P(2)
109.40(14)
116.0(2)
C(1)-Al(2)-Cl(3)
C(1)-Al(2)-Cl(5)
C(1)-P(1)-N(1)
C(1)-P(2)-N(2)
N(1)-Al(1)-Cl(1)
N(2)-Al(1)-Cl(1)
Cl(1)-Al(1)-Cl(2)
Cl(3)-Al(2)-C(4)
Cl(4)-Al(2)-Cl(5)
114.14(12)
115.38(12)
111.94(16)
112.38(16)
113.89(12)
114.49(12)
102.36(7)
106.17(7)
99.60(6)
1.871(3)
1.966(4)
2.1566(18)
2.1665(16)
2.1736(15)
1.728(3)
C(1)-P(2)
1.727(4)
P(1)-N(1)
1.647(3)
P(2)-N(2)
1.639(3)
C(1)-Al(1)a
2.957(3)
Compound 2
Al-Cl(1)
Al-Cl(2)
Al-N(1)
2.1707(9)
2.1688(9)
1.8818(19)
1.885(2)
N(1)-Al-N(2)
Cl(1)-Al-Cl(2)
P(1)-C(1)-P(2)
P(1)-N(1)-Al
P(2)-N(2)-Al
N(1)-P(1)-C(1)
N(2)-P(2)-C(1)
113.88(9)
101.65(4)
123.99(14)
107.81(10)
108.24(10)
108.59(10)
108.00(11)
Al-N(2)
N(1)-P(1)
N(2)-P(2)
C(1)-P(1)
C(1)-P(2)
C(1)-Ala
1.6359(19)
1.6364(19)
1.713(2)
1.708(2)
2.763(3)
Compound 3
Ga-Br(1)
Ga-Br(2)
Ga-N(1)
Ga-N(2)
N(1)-P(1)
2.3529(6)
2.3371(6)
1.937(3)
1.922(3)
1.641(3)
N(1)-Ga-N(2)
Br(1)-Ga-Br(2)
P(1)-C(1)-P(2)
P(1)-N(1)-Ga
P(2)-N(2)-Ga
113.88(14)
105.29(2)
123.0(2)
109.36(17)
109.84(18)
28

N(2)-P(2)
C(1)-P(1)
C(1)-P(2)
C(1)-Gaa
1.642(3)
1.709(4)
1.714(4)
2.913(3)
N(1)-P(1)-C(1)
N(2)-P(2)-C(1)
111.30(18)
110.89(18)
Compound 4
In-Cl(1)
In-Cl(2)
In-N(1)
2.3813(5)
2.3836(5)
2.1370(15)
2.1378(14)
1.6260(15)
1.6260(15)
1.7283(17)
1.7289(17)
2.763(3)
N(1)-In-N(2)
Cl(1)-In-Cl(2)
P(1)-C(1)-P(2)
P(1)-N(1)-In
108.04(6)
100.669(19)
126.62(10)
104.84(7)
104.53(7)
108.47(8)
109.06(8)
In-N(2)
N(1)-P(1)
N(2)-P(2)
C(1)-P(1)
C(1)-P(2)
C(1)-Ina
P(2)-N(2)-In
N(1)-P(1)-C(1)
N(2)-P(2)-C(1)
Compound 5
In-Br(1)
In-Br(2)
In-N(1)
2.5103(4)
2.5240(3)
2.1357(18)
2.1440(18)
1.6293(19)
1.6297(18)
1.720(2)
N(1)-In-N(2)
Br(1)-In-Br(2)
P(1)-C(1)-P(2)
P(1)-N(1)-In
109.95(7)
105.397(11)
126.76(13)
105.38(10)
104.97(9)
In-N(2)
N(1)-P(1)
N(2)-P(2)
C(1)-P(1)
C(1)-P(2)
C(1)-Ina
P(2)-N(2)-In
N(1)-P(1)-C(1)
N(2)-P(2)-C(1)
109.43(10)
109.70(10)
1.730(2)
2.803(3)
Compound 6
Zn-Cl(1)
Zn-Cl(2)
Zn-N
2.2800(5)
2.2558(5)
2.0447(11)
2.0447(11)
1.5887(11)
1.5887(11)
N-Zn-N′
105.87(6)
112.97(2)
119.55(9)
116.84(6)
116.84(6)
110.68(7)
Cl(1)-Zn-Cl(2)
P-C(1)-P′
P-N-Zn
Zn-N′
N-P
P′-N′-Zn
N′-P′
N-P-C(1)
29