Nickel(II) and nickel(0) derivatives of bis(diphenylphosphino)amine: [N(PPh2)2]2Ni, (Ph3P)2Ni[(Ph2P)2NH]. Synthesis, characterization, and some properties

Article abstract of DOI:10.1016/S0022-328X(03)00314-0

Disproportionation of nickel(I) bis(triphenylphosphino)bis (trimethylsilyl)amide, (Ph₃P)₂Ni-N (SiMe₃)₂, in the presence of bis(diphenylphosphino)amine, (Ph₂P)₂NH, yields Ni(II) and Ni(0) phosphinoamide complexes: [N(Ph₂P)₂]₂Ni (1), (Ph₃P)₂Ni[(Ph₂P)₂NH] (2). Ether solution, containing 2 and Ph₃P (1:2) reacts with dioxygen (one equivalent) to form triphenylphosphinoxide adduct (Ph₃P)₂Ni[(Ph₂P)₂ NH·OPPh₃] (3) in high yield. The crystal structures of compounds 1 and 3 have been determined by X-ray diffraction method.

Full text of DOI:10.1016/S0022-328X(03)00314-0

Journal of Organometallic Chemistry 676 (2003) 89Á93
/
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Nickel(II) and nickel(0) derivatives of bis(diphenylphosphino)amine:
[N(PPh2)2]2Ni, (Ph3P)2Ni[(Ph2P)2NH]. Synthesis, characterization,
and some properties
Vyacheslav V. Sushev a, Alexander N. Kornev a,*, Yana V. Fedotova a,
Yurii A. Kursky a, Tatiana G. Mushtina a, Gleb A. Abakumov a, Lev N. Zakharov b,
Arnold L. Rheingold b
a Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, 49 Tropinin Street, 603950 Nizhny Novgorod, Russia
b Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive, La Jolla, CA 92093, USA
Received 14 March 2003; received in revised form 2 April 2003; accepted 17 April 2003
Abstract
Disproportionation of nickel(I) bis(triphenylphosphino)bis(trimethylsilyl)amide, (Ph3P)2Niꢀ/N(SiMe3)2, in the presence of
bis(diphenylphosphino)amine, (Ph2P)2NH, yields Ni(II) and Ni(0) phosphinoamide complexes: [N(Ph2P)2]2Ni (1),
(Ph3P)2Ni[(Ph2P)2NH] (2). Ether solution, containing 2 and Ph3P (1:2) reacts with dioxygen (one equivalent) to form
triphenylphosphinoxide adduct (Ph3P)2Ni[(Ph2P)2NH/
have been determined by X-ray diffraction method.
# 2003 Elsevier Science B.V. All rights reserved.
ꢀ ꢀ ꢀ
/
OPPh3] (3) in high yield. The crystal structures of compounds 1 and 3
Keywords: Transition metals; Nickel; Phosphazanes; Phosphinoamides; X-ray diffraction
1. Introduction
tion of redox and substitution processes. Prolonged
heating of LiN(Ph2P)2 with cobalt(II) or nickel(II)
chlorides in toluene yields phosphazene complexes
bis(Diphenylphosphino)amine (dppa) is one of the
[(Ph2Pꢀ
3MCl2 ꢂ6LiN(PPh2)2
0 [(Ph2PN)2PPh2]2Mꢂ2(Ph2P)3Nꢂ2Mꢂ6LiCl
/
N)2PPh2]2M (Mꢁ
/
Co [4], Ni [5]):
most used and intriguing phosphorusÁnitrogen ligands
/
in transition metal chemistry [1]. It demonstrates
coordinative versatility both in its neutral form and as
an anion [Ph2PNPPh2]ꢀ [1,2]. However, one of the
problems arising is the easy implication of dppa into
redox processes. Particularly, it is specific to the
bis(diphenylphosphino)amide anion [Ph2PNPPh2]ꢀ.
So, lithium salt of dppa reacts with some inorganic
halides to form unpredictable products of phosphazene
type. This is the situation, for example, in the reaction of
LiN(PPh2)2 with PCl3, leading to the mixture of cyclic
(1)
It remains unclear, however, whether homoleptic com-
plexes [N(Ph2P)2]2M were formed in the beginning of
the reaction or not. The same reaction (MꢁNi) in the
/
presence of trimethylphosphine ligands yields dimer 4.
{N(Ph2Pꢁ
/
Pꢀ
/
PPh2)2N},
and
linear
{(Ph2Pꢀ
/
Nꢁ
/
2NiCl2 ꢂ4Me3Pꢂ2LiN(Ph2P)2
PPh2ꢀ)2} phosphazenes [3]. Reactions of nickel and
/
0 f[N(Ph2P)2]Ni(mꢀCl)g2ꢂ2LiCl
(2)
cobalt chlorides with LiN(PPh2)2 represent a combina-
4
Further substitution of the remaining chlorine atom for
dppa is difficult apparently due to considerable steric
* Corresponding author.
0022-328X/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0022-328X(03)00314-0

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V. Sushev et al. / Journal of Organometallic Chemistry 676 (2003) 89Á93
/
hindrances and insolubility of 4. As a part of our studies
on Ni(I) compounds, we investigated the interaction of
nickel(I) bis(triphenylphosphino)bis(trimethylsilyl)a-
mide with dppa.
phosphine (Eq. (7)) or silylamide groups (Eq. (8)):
2(Ph3P)2NiꢀN(SiMe3)2
5
?(Ph3P)4NiꢂfNi[N(SiMe3)2]2g
(6)
(7)
(8)
8
9
(Ph3P)4NiꢂHꢀN(PPh2)2
8
2. Results and discussion
?(Ph3P)2Ni(Ph2P)2NHꢂ2Ph3P
2
2.1. Reactivity
fNi[N(SiMe3)2]2gꢂ2HꢀN(PPh2)2
9
Reaction of nickel silylamide (5) with dppa in molar
ratio 2:3 yields Ni(II)Á
0 [N(Ph2P)2]2Niꢂ2(Me3Si)2NH
/
and Ni(0)Ádppa complexes:
/
1
[N(Ph2P)2]2Ni (1), (Ph3P)2Ni[(Ph2P)2NH] (2) as depicted
in Eq. (3):
The 31P-NMR spectrum of the reaction mixture reveals
the presence of Ph3P (ꢀ4.04 ppm in C6D6) along with
/
two triplets of the Ni(0) complex 2. The formation of 2
according to Eq. (7) was confirmed by 31P-NMR
spectroscopy. Tetrakis(trimethylphosphine)nickel and
dppa to be mixed in C6D6 gave the same signals,
inherent to 2 and Ph3P. Moreover, our attempts to
obtain homoleptic complex, [HN(PPh2)2]2Ni from dppa
and bis(1,5-cyclooctadiene)nickel were unsuccessful.
The color of their mixture in THF changed steadily in
ð3Þ
time from orangeÁ
/
red to blackÁbrown. No defined
/
products were isolated. It was also found that 2 is slowly
decomposed in benzene solution (in sealed NMR tube)
for 2 months.
It seems nickel silylamide 5 may react with dppa in
several different ways. One of the possible initial stages
is the substitution of (Me3Si)2Nꢀ
/
group for (Ph2P)2Nꢀ
/
It should be noted, that homoleptic nickel(II) silyla-
mide (9) does not exist at ambient conditions. The
attempts of its preparation from nickel(II) bromide and
(Me3Si)2NNa in THF gave the mixture of unidentified
products. Furthermore, we ascertained that nickel(I)
silylamide (5) is also labile in solutions.
since dppa has a reactive hydrogen:
(Ph3P)2NiꢀN(SiMe3)2ꢂHꢀN(PPh2)2
5
0 (Ph3P)2Ni[(PPh2)2N]ꢂ(Me3Si)2NH
(4)
6
Freshly prepared concentrated solution of 5 in
toluene, diethyl ether or methylene chloride1 at 5Á
The another version of the possible initial stage may be
the substitution of two triphenylphosphine ligands for
bidentate dppa ligand:
/
10 8C has pale-yellow color and absorption at 438 nm
in electronic spectra. It was noted that optical density of
the solutions rises (!) under dilution at first time.
Moreover, after dilution the electronic spectra contained
four absorption bands 378, 417, 462 and 543 nm. The
same bands occurred after prolonged exposition of more
concentrated solutions for a 2 weeks. We cannot
separate any defined products from this solution. An
ESR signal of 5 disappeared and recovery of 5 was also
impossible. These observations lead us to a supposition
that disproportionation and dissociation processes may
take place in the solutions of nickel(I) silylamide (5).
Since the Ni(0) compound 2 contains two different
ligands (Ph3P and HN(PPh2)2) we decide to clarify
which of the ligands being coordinate to Ni atom is
more sensitive to oxidation. One equivalent of dioxygen
(1/2 mol) per mol of 2 was added to a mixture contain-
(Ph3P)2NiꢀN(SiMe3)2ꢂHꢀN(PPh2)2
5
0 [HN(Ph2P)2NiꢀN(SiMe3)2]ꢂ2Ph3P
(5)
7
In both reactions we should have obtained new com-
pounds (6, 7) of monovalent nickel. However, an ESR
signal of these complexes was not detected in the course
of the reaction while the starting signal of 5 is merely
diminished until disappearance. These results are con-
sistent with known data indicating that small chelate
angle at nickel atom is unfavorable for existence and
formation of Ni(I) complexes [6]. So, the electrochemical
reduction of the similar nickel(II) complex containing
the ligand of small bite size, [CH2(Ph2P)2]2Ni[BF4]2,
does not give any defined products [6].
This circumstance leads us to the conjecture of
another possible and most probable reaction path
including disproportionation of starting nickel silyla-
mide (Eq. (6)) follows by the substitution of triphenyl-
1
Methylene chloride slowly reacts with nickel silylamide 5 on the
sunlight. Full decoloration observed for 1 h.

V. Sushev et al. / Journal of Organometallic Chemistry 676 (2003) 89Á
/
93
91
Table 1
Summary of crystal and refinement data for complexes
mixture at room temperature instantly affords a lot of
colorless crystals of pure triphenylphosphine oxide. No
other
free
phosphine
oxides
(particularly
[N(PPh2)2]2Ni (1)
(Ph3P)2Ni[(Ph2P)2-
NH OPPh3] (3)
ꢀ ꢀ ꢀ
Ph2PNHP(O)Ph2, possible products of dppa oxidation)
were detected.
/
/
Empirical formula
Formula weight
Temperature (K)
C48H40N2NiP4
827.41
150(2)
C78H66NNiOP5
1246.88
150(2)
˚
Wavelength (A)
2.2. Structures
0.71073
monoclinic
I2/a
0.71073
triclinic
Crystal system
Space group
Unit cell dimensions
¯
P1
/
The structures of 1 and 3 have been determined by X-
ray diffraction methods. The crystal data and some
details of the data collection and refinement for 1 and 3
are given in Table 1. Selected bond distances and angles
for 1 and 3 are in Tables 2 and 3, respectively.
The Ni atom in 1 is on a center of symmetry; i.e. the
NP2NiP2N fragment is planar (Fig. 1). In 3 the Ni atom
has a distorted tetrahedral environment (Fig. 2). The
˚
a (A)
17.5853(8)
12.3427(6)
18.5459(9)
90
13.0058(7)
13.3297(8)
19.5573(11)
76.8900(10)
80.1530(10)
78.8340(10)
3210.9(3)
2
˚
b (A)
˚
c (A)
a (8)
b (8)
96.5050(10)
90
g (8)
3
V (A )
˚
3999.5(3)
4
1.374
Z
Dcalc (Mg mꢀ3
Absorption coefficient
)
1.290
0.474
Nꢀ
/
P bond lengths in a free (Ph2P)2NH molecule are
˚
1.692(2) A [7]. The close distances [1.6916(18) and
0.683
(mmꢀ1
)
˚
1.6935(18) A] were observed in Ni(0) complex 3. So
the chelation of dppa to the nickel atom in 3 does not
change the length and the order of NꢀP bond. At the
same time the valence PNP angle is contracted signifi-
Crystal size (mm3)
0.25ꢃ
/
0.20ꢃ
/
0.10
0.35ꢃ
/
0.30ꢃ0.25
/
Reflections collected
Independent reflections
12152
4590
20623
14378
/
[Rint
ꢁ/
0.0169]
[Rint
ꢁ/0.0190]
Absorption correction
SADABS
SADABS
cantly from 118.9(2)8 in the free ligand [7] to 101.97(10)8
Max. and min. transmis- 1.000; 0.898
sion
1.000; 0.837
in the Ni(0) complex 3. The average Niꢀ
/
P distance of
˚
2.22 A in 1 is within the typical range observed for Ni(II)
complexes and slightly longer than those (2.1926(6) and
Refinement method
Full-matrix least-
squares on F2
4590/0/395
Full-matrix least-
squares on F2
14378/0/779
˚
2.1987(5) A) founded in Ni(0) complex 3.
In going from 1 to 3 we observed the shortening of the
Data/restraints/para-
meters
Final R indices
Rꢁ
wRꢁ
Rꢁ
0.1269 a,
wRꢁ
0.3397 b
1.154
0.890;ꢀ
/
0.1260 a,
0.3394 b
Rꢁ
wRꢁ
R1ꢁ
0.0559 a,
wRꢁ
0.1122 b
1.014
0.618; ꢀ
/
0.0438 a,
0.1053 b
˚
N bonds from 1.6935(18) and 1.6916(18) A to
Pꢀ
/
[I ꢀ/2s(I)]
/
/
˚
1.653(7) and 1.656(9) A, respectively. This can be
P bonds
when the metal center is more electropositive, as
R indices (all data)
/
/
rationalized by a higher bond order of the Nꢀ
/
/
/
c
S
Largest difference peak
ꢀ3
/1.630
/0.608
electron density is transferred from the metal to appro-
˚
and hole (e A
)
priate NꢀP p-bonding orbitals. It causes in turn further
/
decreasing of PNP and chelating PNiP angles to 96.5(4)
and 67.43(8)8, respectively. To the best of our knowl-
edge, the chelating PNiP angle 67.43(8)8 in 1 is the
smallest known. For example, in the similar compound
[CH2(PPh2)2]2Ni[BF4]2 [6] chelating PNiP angle is sig-
nificantly larger, 73.2(3)8. Interestingly, the complex 1 is
paramagnetic at room temperature with magnetic mo-
ment 3.1 mB, while the other planar phosphine com-
plexes are diamagnetic [6]. Perhaps, this phenomenon is
associated with temperature dependent change in geo-
a
Rꢁ
/
ajjFojꢀ
wRꢁ
R(wF2)ꢁ
(aP)2ꢂ [2Fc2ꢂ
bP], Pꢁ
Sꢁ
Goodness-of-fit on F2ꢁ
/
jFcjj/ajFoj.
{a[w(Fo2ꢀ
max(Fo,0)]/3.
{a[w(Fo2ꢀ
b
/
/
/
Fc2)2]/a[w(Fo2)2]}1/2
;
wꢁ
/
1/[s2(Fo2)ꢂ
/
/
/
/
c
/
/
/
Fc2)2]/(nꢀ
/
p)}1/2, where n
is the number of reflections, and p is the number of refined parameters.
ing 2 and triphenylphosphine (reaction mixture after
separation of the complex 1). To our surprise we
succeeded to separate not a free oxidized ligands but
in the complex with 2. The compound 3 contained
Ph3Pꢁ
/
O molecule associated with hydrogen atom of
O
Table 2
dppa ligand by hydrogen bond. Since the Ph3Pꢁ
/
˚
Selected bond lengths (A) and angles (8) for [N(PPh2)2]2Ni (1)
molecule was not coordinate to a nickel atom, the
oxidation process may conditionally consider as cataly-
tic one.
Ni(1)ꢀ
Ni(1)ꢀ
/
P(1)
P(2)
2.226(2)
2.222(2)
1.653(7)
1.822(9)
1.832(9)
2.469(3)
1.656(9)
P(2) a1ꢀ
P(2)ꢀNi(1)ꢀ
N(1)ꢀP(1)ꢀ
N(1)ꢀP(2)ꢀ
P(1)ꢀN(1)ꢀ
/
Ni(1)ꢀ
/
P(1)
112.57(8)
67.43(8)
98.0(3)
/
/
/
P(1)
P(1)ꢀ
P(1)ꢀ
P(1)ꢀ
P(1)
P(2)ꢀ
/
N(1)
C(1)
C(7)
/
/
Ni(1)
Ni(1)
P(2)
(Ph3P)2Ni[(Ph2P)2NH]
2
/
/
/
98.0(3)
/
/
/
96.5(4)
1=2O2
0 (Ph3P)2Ni[(Ph2P)2NH ꢀ ꢀ ꢀ OꢁPPh3]
/
ꢀ ꢀ ꢀ
/P(2)
(9)
Ph3P
/N(1)
3
a
Symmetry equivalent atom.
Addition of an excess of dioxygen to the reaction

92
V. Sushev et al. / Journal of Organometallic Chemistry 676 (2003) 89Á93
/
Table 3
˚
Selected bond lengths (A) and angles (8) for (Ph3P)2Ni[(Ph2P)2NH
OPPh3] (3)
/
ꢀ ꢀ ꢀ
/
Ni(1)ꢀ
Ni(1)ꢀ
Ni(1)ꢀ
Ni(1)ꢀ
/
P(1)
P(2)
P(3)
P(4)
2.1736(6)
2.1741(6)
2.1926(6)
2.1987(5)
P(1)ꢀ
P(1)ꢀ
P(2)ꢀ
P(1)ꢀ
P(2)ꢀ
P(3)ꢀ
N(1)ꢀ
N(1)ꢀ
P(4)ꢀN(1)ꢀ
P(4)ꢀN(1)ꢀ
P(3)ꢀN(1)ꢀ
N(1)ꢀ
/
Ni(1)ꢀ
Ni(1)ꢀ
Ni(1)ꢀ
Ni(1)ꢀ
Ni(1)ꢀ
Ni(1)ꢀ
P(4)ꢀ
P(3)ꢀ
/
P(2)
P(3)
P(3)
P(4)
P(4)
P(4)
113.77(2)
112.92(2)
118.35(2)
116.25(2)
116.26(2)
73.59(2)
92.13(6)
92.29(6)
/
/
/
/
/
/
/
/
/
/
/
P(3)ꢀ
P(3)
ꢀ ꢀ ꢀ
P(4)ꢀ
P(5)ꢀ
P(5)ꢀ
N(1)ꢀ
O(1)
ꢀ ꢀ ꢀ
N(1)
ꢀ ꢀ ꢀ
/N(1)
1.6935(18)
2.6301(7)
1.6916(18)
1.444(2)
1.808(2)
0.83(2)
/
/
/
/P(4)
/
/
Ni(1)
Ni(1)
P(3)
/
N(1)
O(1)
C(73)
/
/
/
/
/
101.97(10)
128.8(16)
128.9(16)
170(2)
/
/
/
H(1N)
/
H(1N)
H(1N)
O(1)
/
/
H(1N)
/
/
1.99(2)
2.820(3)
/
H(1N)
/
ꢀ ꢀ ꢀO(1)
/
/
/
Fig. 2. An ORTEP view of 3 with 30% probability ellipsoids.
under an argon atmosphere using standard Schlenk
techniques.
Spectrophotometric determination of nickel with
dimethylglioxime was provided by the method [11];
Infrared spectra were recorded on a PerkinÁElmer
/
577 spectrometer from 4000 to 400 cmꢀ1 in nujol.
Room-temperature magnetic moments were mea-
sured by the Faraday method.
NMR spectra were recorded in CDCl3 or C6D6
solutions using ‘Bruker DPX-200’ instrument, with
Me4Si as internal standard.
3.2. Reaction of (Ph3P)Niꢀ
/
N(SiMe3)2 with
bis(diphenylphosphino)amide
A mixture of toluene solutions of (Ph2P)2NH (0.29 g,
0.75 mmol, 5 ml) and (Ph3P)2NiꢀN(SiMe3)2 (0.37 g,
/
0,50 mmol, 5 ml) was maintained at 20 8C. The yellow
mixture turned dark-red. Red crystalline precipitate of 1
was formed after 3 h. It was filtered, washed with
toluene and dried in vacuum. Yield 0.15 g (73%). Anal.
Calc. for C48H40P4N2Ni (1): C, 69.67, H, 4.87, Ni, 7.09.
Found: C, 70.00; H, 5.04, Ni, 6.93%. IR (cmꢀ1): 1430 s,
1300 w, 1220 w, 1180 vw, 1100 s, 1020 w, 1000 w, 920 vs,
Fig. 1. An ORTEP view of 1 with 30% probability ellipsoids. Only one
position of the disordered Ph-rings is shown.
metry of 1 from tetrahedral (at room temperature) to
plane-square at 150 K. This study now is in progress.
870 s, 730 s, 700 s, 550 s, 510 s, 490 s. meff
ꢁ3.1 mB.
/
Toluene was pumped in vacuum from filtrate and
changed for ether (8 ml). Dark-brown crystals of 2
formed overnight were filtered, washed with cold ether
3. Experimental
3.1. General considerations
and dried in vacuum. Yield 0.18
g (75%) of
(Ph3P)2Ni[(Ph2P)2NH]. Anal. Calc. For C60H51P4NNi:
C, 74.40; H, 5.31; Ni, 6.06. Found: C, 74.56; H, 5.43; Ni,
5.93%. IR (cmꢀ1): 3050 w, 1580 w, 1430 m, 1300 m,
1200 m, 1180 m, 1120 m, 1090 s, 1070 w, 1020 m, 790 m,
730 s, 700 vs, 550 m, 510 vs. 31P-NMR (C6D6), d ppm:
Solvents were purified following standard methods
[8]. Toluene was thoroughly dried and distilled over
P2O5 prior to use. Ether was dried and distilled over Na/
benzophenone; the compounds (Ph3P)2Niꢀ
/N(SiMe3)2
[9], (Ph2P)2NH [10], were prepared according to known
methods. All manipulations were performed with rigor-
ous exclusion of oxygen and moisture, in vacuum or
2
2
1
61,9 (t, JPP 20.3, Ph2P), 33.5 (t, JPP 20.3, Ph3P), H-
NMR: 2.2 (s, 1H, NH), 6.3Á8.1 (m, 50H).
/

V. Sushev et al. / Journal of Organometallic Chemistry 676 (2003) 89Á
/
93
93
3.3. Oxidation of 2 in the presence of Ph3P
tion of novel dppa complexes of nickel, [N(Ph2P)2]2Ni
(1), (Ph3P)2Ni[(Ph2P)2NH] (2). The molecule of
bis[bis(diphenylphosphino)amido]nickel (II) (1) shows
the smallest of known chelating PNiP angle 67.43(8)8
and possess of magnetic moment 3.1 mB at 20 8C. The
partial oxidation of 2 with dioxygen in the presence of
Ph3P affords hydrogen bonded triphenylphosphine
The reaction of (Ph2P)2NH (0.75 mmol) with
(Ph3P)2Niꢀ/N(SiMe3)2 (0.50 mmol) was carried out as
described above. The toluene filtrate after separation of
1 contained 0.25 mmol of 2 and 0.5 mmol of Ph3P.
Toluene was changed for ether. Dioxygen (2.8 ml, 0.125
mmol) was allowed to react with solution at 20 8C.
oxide adduct {Ph3PO
dation of 2 with an excess of O2 affords pure triphenyl-
phosphine oxide.
/
ꢀ ꢀ ꢀ
/
HN(PPh2)2Ni(PPh3)2} (3). Oxi-
Large brownÁ
/
red crystals were grown overnight. The
crystals were separated, washed with cold ether and
dried in vacuum. Yield 0.24 g (77%) of 3. Anal. Calc.
For C78H66P5NONi: C, 75.13; H, 5.34; Ni, 4.71. Found:
C, 74.96; H, 5.40; Ni, 4.75%. IR (cmꢀ1): 1430 m, 1170 s
5. Supplementary material
(Pꢁ
/
O), 1120 m, 1080 m, 1020 w, 970 w, 820 m, 740 w,
720 m, 700 s, 540 s, 510 s. 31P-NMR (C6D6), d ppm:
61,9 (t, 2JPP 19.7 Hz, Ph2P), 33.6 (t, 2JPP 19.7 Hz, Ph3P),
Crystallographic data have been deposited with the
Cambridge Crystallographic Data Centre, CCDC
204878 for 1 and CCDC 204879 for 3. Copies of this
information may be obtained free of charge from The
Director, CCDC, 12, Union Road, Cambridge CB2
27.3 (s, Ph3PO). 1H-NMR: 2.3 (s, 1H, NH), 6.3Á
8.1 (m,
65H).
/
3.4. X-ray diffraction studies
1EZ, UK (Fax: ꢂ44-1223-336033); e-mail deposit@
/
ccdc.cam.ac.uk or http://www.ccdc.cam.ac.uk.
X-ray data were collected on a Bruker Smart Apex
CCD diffractometer at 150(2) K. The crystal data and
some details of the data collection and refinement for 1
and 3 are given in Table 1. Both structures were
determined using a combination of direct methods and
calculations of Fourier maps and refined by full-matrix
least-squared procedures based on the structural factors
F2. The positions of the H atoms were calculated using
general geometrical conditions and the H atoms were
refined in a rigid group model. Selected bond distances
and angles in 1 and 3 are given in Tables 2 and 3,
respectively. In the crystal structure of 1 there are two
possible arrangements of the main molecule with
different positions of Ph-rings. The disordered positions
of Ph-rings corresponding to two such arrangements
were found from the difference F-map and refined
without additional restrictions for Ph-rings. Occupation
multiplicities of these two arrangements were refined
and gave ratio 49/51. The high value of R-factor for this
structure seems to be related with existance of such
disorder.
Acknowledgements
We are grateful to the Russian Foundation for Basic
Research (Grant 03-03-32051 and 1649.2003.3) for
financial support of this work.
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4. Conclusions
Nickel (I) bis(triphenylphosphino)bis(trimethylsilyl)a-
mide turned out to be a convenient reagent in prepara-
[13] G. Sheldrick, Bruker XRD, Madison, WI, USA.