DFT study and dynamic NMR evidence for cis-trans conformational isomerism in square planar Ni(II) thioselenophosphinate, Ni(SeSPPh2) 2

Article abstract of DOI:10.1016/j.jorganchem.2014.06.013

Theoretical (DFT) and experimental (dynamic NMR) study of cis-trans conformational isomerism in Ni(II) square planar thioselenophosphinate, Ni(SeSPPh₂)₂, have been carried out. The DFT investigation [B3LYP/6-311++G(d,p), gas] of this

Full text of DOI:10.1016/j.jorganchem.2014.06.013

Journal of Organometallic Chemistry 768 (2014) 151e156
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
DFT study and dynamic NMR evidence for cis-trans conformational
isomerism in square planar Ni(II) thioselenophosphinate,
Ni(SeSPPh2)2
,
**
Alexander V. Artem'ev a, Vladimir A. Shagun a, Nina K. Gusarova a, C.W. Liu b
,
,
, *
Jian-Hong Liao b, Yurii V. Gatilov c d, Boris A. Trofimov a
a A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky Str., 664033 Irkutsk, Russian Federation
b Department of Chemistry, National Dong Hwa University, Hualien, Taiwan 97401, Republic of China
c N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, 9 Lavrentiev Ave.,
630090 Novosibirsk, Russian Federation
d Novosibirsk State University, 2 Pirogova Str., Novosibirsk 630090, Russian Federation
a r t i c l e i n f o
a b s t r a c t
Article history:
Theoretical (DFT) and experimental (dynamic NMR) study of cis-trans conformational isomerism in Ni(II)
square planar thioselenophosphinate, Ni(SeSPPh2)2, have been carried out. The DFT investigation [B3LYP/
6-311þþG(d,p), gas] of this complex reveals that its cis-to-trans isomerization occurs through two
minimal energy crossing points (MECPs) located at the intersection of the lowest singlet and triplet PESs
(potential energy surfaces). The calculated relative energies of the MECPs, 5.6 and 3.6 kcal/mol, corre-
spond to low-energy barriers of “cis-Ni(SeSPPh2)2 [S] # pseudoterahedral-Ni(SeSPPh2)2 [T]” and “trans-
Ni(SeSPPh2)2 [S] # pseudoterahedral-Ni(SeSPPh2)2 [T]” spin crossover rearrangements. The dynamic 31P
NMR study of Ni(SeSPPh2)2 is fully confirms these computations: below 208 K, the cis- and trans-isomers
are in a dynamic equilibrium. The free energy of activation for this fluxional process calculated from the
Received 1 March 2014
Received in revised form
21 May 2014
Accepted 16 June 2014
Available online 8 July 2014
Keywords:
Nickel
DFT calculations
coalescence temperature is
D
Gs ¼ 11.5 kcal/mol.
VT 31P NMR
© 2014 Elsevier B.V. All rights reserved.
Spin-crossover
Thioselenophosphinate
Introduction
Obviously, structural information such as calculations of
geometrical and electronic configurations, molecular dynamics as
well as thermodynamic and magnetic properties of the dichalco-
genophosphinato complexes is an important basis for under-
standing the different factors influencing their practically useful
properties. For example, structural investigations of metal dichal-
cogenophosphinates can provide insight into the complex pro-
cesses occurring at the liquideliquid extraction of metals as well as
can be helpful for the design of more selective extractants for metal
separation, e.g. LnIII and AnIII [8]. In this field, there are series of
works devoted to DFT and ab initio computations of metal dithio-
phosphinates (lanthanides and actinides [9], Co and Ni [10], Au [11],
Na [12]) and, in a less degree, diselenophosphinates (Ce, Nd, Th, Pa,
U, Np, Pu) [13].
More recently, developing the chemistry of thio-
selenophosphinic acids, we have identified an interesting structural
feature for the solid state structure of Ni(II) thio-
selenophosphinates, Ni(SeSPR2)2, (R ¼ Ph or CH2CH2Ph) [5a].
Namely, the chalcogen atoms of square planar Ni(SeS)2 unit, ac-
cording to X-ray diffraction analysis, are disordered over the two
positions. For this reason, it is unclear what isomer (cis-, trans- or
Metal dichalcogenophosphinates represent an important class
of organophosphorus compounds that are widely used both in in-
dustry and academic research [1]. Among them, the most signifi-
cant are metal dithiophosphinates, which are frequently applied as
intermediate forms in selective liquideliquid extraction of metal
ions [2] as well as flotation reagents [3]. Less attention has been
paid to the diselenophosphinates [4] and, especially, thio-
selenophosphinates [5], however, their chemistry is developing
rapidly. Coordination chemistry of dichalcogenophosphinates has a
distinctive structural diversity due to their abilities to form unique
molecular structures (mono-, bi-, tetra-, hexa-, octa-, etc.) [1,4,6],
many of which are effective single-source precursors to semi-
conductive metal selenides nanocrystals [7].
* Corresponding author. Tel.: þ7 395242 14 11; fax: þ7 395241 93 46.
** Corresponding author. Tel.: þ86 886 3 8633607; fax: þ86 886 3 8633570.
E-mail addresses: chenwei@mail.ndhu.edu.tw (C.W. Liu), boris_trofimov@irioch.
irk.ru (B.A. Trofimov).
http://dx.doi.org/10.1016/j.jorganchem.2014.06.013
0022-328X/© 2014 Elsevier B.V. All rights reserved.

152
A.V. Artem'ev et al. / Journal of Organometallic Chemistry 768 (2014) 151e156
their mixture) forms the crystal packing? Furthermore, the
Ni(SeSPR2)2 complexes are expected to undergo interconversion in
solution state. Indeed, it is known that the chelate complexes
M(A^B)2 where A^B are flexible bidentate ligands can adopt
different conformations, which are often in a dynamic exchange
[14]. In particular, for square planar Ni(II) complexes, an inversion
of the A^B ligands through a tetrahedral intermediate is specific
(spin-crossover equilibrium) [14d,15], which should lead to a
conformational isomerism of cis-trans type (Scheme 1). Moreover,
in solution these isomers can be detected by NMR spectroscopy, if
the rate of the exchange is appropriate for NMR time scale [15,16].
At the same time, in the literature, to our surprise, there are no data
on existence of the cis-trans isomerism for square planar Ni(II)
complexes bearing thiophosph(in)ate [O(S)PR2] ligands, not to
mention selenophosph(in)ates [O(Se)PR2], thioselenophosph(in)
ates [S(Se)PR2] or related ligands (thiocarboxylates, selenocarbox-
ylates and thioselenocarboxylates).
In continuation of our research into selenophosph(in)ato metal
complexes, we have investigated the possibility of cis-trans
conformational isomerization within Ni(II) thioselenophosphinato
complex [Ni(SeSPPh2)2]. Accordingly, the main questions addressed
in this work are (i) to provide insight into detailed mechanism of
this process using DFT calculations and, (ii) to verify experimentally
(by dynamic 31P NMR spectroscopy) the equilibrium between two
isomeric forms. Concurrently, herein we report an original one-pot
method for the synthesis of these complexes and crystal structure
of one from them.
Scheme 2. One-pot synthesis of complexes 2aec. Conditions: i. 35e40 ꢀC, 30 min; ii.
23e25 ꢀC, 5 min; iii. 23e25 ꢀC, 5 min.
ligands. The selenium and sulfur atoms are disordered over two
positions in 0.716(1):0.284(1) ratio with the retention of cis atomic
arrangement of selenium. The bond lengths of NieS and NieSe are
consistent with those in square planar complexes 2a,b [5a] and
tetrahedral complex Ni[iPr2P(S)NP(Se)iPr2]2 [20], in which S and Se
atoms are also disordered. Within the extended structure of 2c,
between neighboring molecules there are weak intermolecular
C(8)-H … Se(2) [2.82 Å, 148ꢀ] and
p(O4CCCC) … p(O4CCCC) [Cg …
Cg 3.609(2), dpl 3.505 Å] interactions.
Theoretical study
Obviously, cis-to-trans rearrangement of diamagnetic (S ¼ 0)
square-planar Ni(SeSPPh2)2 complex occurs via pseudotetrahedral
paramagnetic (S ¼ 1) forms A, Scheme 3. It was shown earlier
[14d,21], that the diagonal twist mechanism of rotation rear-
rangement within bis-chelate complexes is more energetically
favorable than the bond rupture-formation pathway. Taking this
into consideration, we have constructed B3LYP/6-311þþG(d,p)
energy profile of the rotation isomerization of model complex
Ni(SeSPPh2)2 (2a) for singlet and triplet states along the exo-Se-Ni-
Results and discussion
One-pot synthesis of complexes 2aec
Usually, transition metal thioselenophosphinates are prepared
by ion exchange between alkali metal [17] or ammonium thio-
selenophosphinates [18] and metal salts. We have elaborated facile
and efficient one-pot synthesis of Ni(II) thioselenophosphinates
from available [19] secondary phosphines 1aec (Scheme 2). So, the
latter are treated with powdered selenium in benzene solution
(35e40 ꢀC, 30 min) to give secondary phosphine selenides R2P(Se)
H, which further react (without isolation) with S8/NaOH system
(stoichiometric ratio, ethanol, 23e25 ꢀC, 5 min) to provide sodium
thiselenophosphinates. Finally, NiCl2 is added to the resulting thi-
oselenophosphinates to afford the target complexes 2aec in
69e81% yields.
S twisting angle (b, deg). For this purpose, methods developed by
Harvey [22] for the study of mechanisms associated with the spin-
state changing are applied. This approach is based on the deter-
mination of minimum energy crossing points (MECPs) on the seam
of intersecting lowest singlet and triplet PESs. Recently, this pro-
cedure has been successfully employed to establish the spin-
forbidden isomerization pathways for several bis-chelate Ni(II)
complexes [23].
The energy profiles for the conformational isomerization of 2a
as the function of the twisting angle b are shown in Fig. 2. The value
of this angle within trans-isomer is taken as the starting point
Complexes 2aec have been characterized by solution 1H, 31P,
77Se NMR spectroscopy. The elemental analyses of the compounds
support their compositions. The complexes 2a,b were characterized
previously by X-ray crystallography [5a], while the structure of
earlier unknown complex 2c was determined for the first time. The
crystals of 2c contain discrete monomeric molecules (Fig. 1),
exhibiting square planar Ni(SSe)2 cores, in which the Ni(II) ion is
chelated by two sulfur and two selenium atoms in the equatorial
plane (deviations from the mean plane being 0.056 Å). Thus, the
both thioselenophosphinate anions act as S,Se-bidentane (h2
)
Fig. 1. Molecular structure of 2c with 50% probability ellipsoids (minor disorder S and
Se atoms omitted for clarity). Selected bond lengths (Å) and bond angles (deg): Ni(1)-
Se(1) 2.3666(6), Ni(1)-Se(2) 2.3487(6), Ni(1)-S(1) 2.2990(7), Ni(1)-S(2) 2.2741(8), PeSe
2.1462(9), 2.1503(9), PeS 2.106(1), 2.088(1), PeC 1.809(3) e 1.819(3), Se(1)-Ni(1)-Se(2)
91.56(2), S(1)-Ni(1)-S(2) 86.99(3), S(1)-Ni(1)-Se(1) 91.25(2), S(2)-Ni(1)-Se(2) 90.28(2).
Scheme 1. Cis-to-trans conformational isomerization for square planar Ni(A^B)2
complexes proceeding via spin-crossover equilibrium.

A.V. Artem'ev et al. / Journal of Organometallic Chemistry 768 (2014) 151e156
153
The gradient descent from the
М
ЕСР1 along the singlet and
triplet PESs leads to two minima which correspond to cis-2a(S) and
pseudotetrahedral-2a(T) structures (Fig. 2). The similar procedure
performed for
2a(T) structures.
Thus, the calculated relative energies of the
(5.6 and 3.6 kcal/mol) represent the activation barriers for “cis-
2a # pseudoterahedral-2a” and “trans-2a # pseudoterahedral-2a”
stereoisomerizations, respectively. Simplistically, cis-to-trans
isomerization of Ni(SeSPPh2)2 is associated with overcoming of two
activation barriers, 5.6 and 2.5 kcal/mol. Considering these values,
we have concluded that the conformational isomerization of
Ni(SeSPPh2)2 complexes is rather probable process.
МЕСР2 leads to trans-2a(S) and pseudotetrahedral-
М
ЕСР1 and МЕСР2
Scheme 3. A tentative pathway for interconversion of square-planar complex 2a.
(
b
¼ 0). The structures corresponding to the stationary points
appeared on the singlet (S) and triplet (T) PESs are pictured in Fig. 3,
while the energy data related to for key structures are collected in
Table 1.
On the singlet PES there are two minima corresponding to cis-
and trans-square-planar isomers, cis-2a and trans-2a, having a
minor difference in energy. The trans-isomer is found to be slightly
stable than the cis-isomer by 0.3 kcal/mol. On the triplet PES, the
complex 2a is stabilized in a pseudotetrahedral conformation,
pseudotetrahedral-2a (T), the relative energy of which is 1.1 kcal/
mol (Table 1, Fig. 2).
In the singlet state, trans-to-cis rearrangement [trans-
2a(S) / cis-2a(S)] is associated with overcoming the activation
barrier in the 25.6 kcal/mol. The structure of the corresponding
transition state, TS1, is depicted in Fig. 2. The rotation isomerization
of the pseudotetrahedral structure on the triplet PES could poten-
tially occurs through the two channels, i.e. either via planar state
having cis-oriented chalcogen atoms (TS2) or state with trans-
disposed S and Se atoms (TS3). The first pathway is attributed to
with overcoming the activation barrier in the 5.4 kcal/mol, while
the second channel requires overcoming the barrier in 2.7 kcal/mol
(Figs. 2 and 3, Table 1).
VT 31P NMR study of complex 2a
To verify the predicted cis-trans interconversion for Ni(II) thio-
selenophosphinates, we have undertaken VT 31P NMR study of the
complexes 2a in CD2Cl2 solution over the temperature range
from ꢁ90 to 18 ꢀC. At ambient temperature 1H NMR spectrum of 2a
reveals characteristic peaks corresponding to organic groups of the
ligands. The 31P NMR spectrum shows a slightly broad peak at
56.44 ppm flanked by a pair of blurry satellites due to the 31Pe77Se
splitting (Fig. 4). Upon cooling of the solution, the peak becomes
broad and maximum of broadening is at ꢁ65 ꢀC (coalescence
temperature). At ꢁ80 ꢀC, new broad peaks emerge at 58.81 and
60.11 ppm (in integral ratio of ~1:1) along with small medial peak at
58.42 ppm, which is caused by overlapping of 77Se satellites from
major peaks. On further decreasing the temperature to ꢁ90 ꢀC, the
spectrum of 2a contains two signals (59.08 and 60.48 ppm) as well
as minor peak (59.75 ppm) from the overlapping 77Se satellites.
These results indicate that the fluxional process within complex 2a
slows down upon lowering the temperature.
The existence of two non-generative stationary states on the
singlet PES leads to formation of two multidimensional seams of
crossing between the singlet and the triplet PESs. The intersection
of the two curves occurs at the
А1 and А2 regions, where the
This observation is clearly indicates on predicted interconver-
sion between cis- and trans-isomers of complex 2a. The 31P NMR
chemical shifts of the individual isomers are different
below ꢁ80 ꢀC, however, at higher temperatures, when the ex-
change of the spin state (crossover) for cis-2a and trans-2a com-
plexes takes place. The minimal energy reaction paths including the
spin-crossover are shown in Fig. 2 as double lines passed through
А
1 and
А
2 regions. To find the MECPs, the geometries of structures
1 and 2 regions are taken as the initial guesses.
change rate is high, a single averaged signal is observed. Using the
pffiffiffi
located at the
А
А
Gutowski-Holm approximation kc
¼
p
*
Dn
/
2(where Dn is differ-
The optimizations of these structures are performed until the en-
ergy differences for the singlet and triplet states do not exceed
ence between the 31P chemical shift of two peaks) [24], the rate
constant, kc, for the equilibrium process is calculated. The free en-
0.00003 and 0.000005 a.u. for
М
ЕСР1 and
within
М
М
ЕСР2, respectively.
ЕСР1 and ЕСР2
ergy of activation, calculated based on Eyring equation
D
Gs ¼ RTc
The values of the dihedral angle
b
М
[lnTc e lnkc þ 23.76] [24,25] (where Tc is coalescence temperature,
i.e. 208 K), is ca. 11.5 kcal molꢁ1. This value is quite comparable with
the predicted one: a discrepancy is caused by influence of the
solvent.
structures are 162 and 19ꢀ (Fig. 3).
Conclusions
To summary, by using DFT computations combined with dy-
namic NMR spectroscopy, we have clearly established the cis-trans
conformational isomerism for square planar complex Ni(SeSPPh2)2.
It has been computed that the cis-to-trans isomerization of
Ni(SeSPPh2)2 proceeds via triplet pseudotetrahedral intermediate.
This transition is associated with overcoming of two minimal
activation barriers, 5.6 and 2.5 kcal/mol, which energetically
correspond to
МЕСР1 and МЕСР2 states on intersecting singlet
and triplet PESs. The predicted phenomenon is fully confirmed by
dynamic 31P NMR spectroscopy, i.e. cis- and trans-isomers of the
complexes 2a are presented in solution below 208 K. At higher
temperature, the rate of the cis-trans interconversion is faster than
the NMR time scale, so the both isomers appear to be identical. The
data obtained are essential complement to the coordination and
inorganic chemistry.
Fig. 2. Energy profile for the trans # cis stereoisomerization of Ni(SeSPPh2)2 (2a)
shown as the functions of the exo-S-Ni-Se twisting angle ( , deg). The solid line for the
singlet PES; dashed line for the triplet PES; double solid for the spin forbidden
reactions.
b

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A.V. Artem'ev et al. / Journal of Organometallic Chemistry 768 (2014) 151e156
Fig. 3. Optimized structures and selected metrics for key states of Ni(SeSPPh2)2 (2a) stereoisomerization calculated by B3LYP/6-311þþG(d,p) method (bond lengths and angles are
given in Å and degrees).
Experimental
all stationary points. Transition states were located on the PESs
using quadratic synchronous transit (QST) method [28]. All calcu-
lations were performed for isolated molecules.
Computational details
The DFT calculations were carried out in Gaussian 09 package
[26] using the B3LYP functional [27] and 6-311þþG(d,р) basis set.
Minimum energy structures were found by steepest descent path
(gradient line) optimization from transition states or from the
MECP to a neighboring stationary point. Harmonic vibrational
frequencies were calculated at the same level of theory to identify
One-pot synthesis of complexes 2aec
To a solution of freshly distilled secondary phosphine 1aec
(1 mmol) in benzene (12 mL), powdered selenium (79 mg, 1 mmol)
was added and the mixture was stirred at 35e40 ꢀC until the
dissolution of Se (ca. 30 min). In this solution, powdered sulfur S8

A.V. Artem'ev et al. / Journal of Organometallic Chemistry 768 (2014) 151e156
155
Table 1
Total energies (Etot), total energies with the account for zero point energy (Etot þ ZPE) and relative energies (
isomerization calculated by B3LYP/6-311þþG(d,p) method.
D
Е and DЕtot þ ZPE), for key states of Ni(SeSPPh2)2 (2a) stereo-
Structure
Multiplicity
Etot (а.u.)
DЕ
Etot þ ZPE
DЕtot þ ZPE (Kcal/mol)
(Kcal/mol)
(а.u.)
cis-2a
trans-2a
pseudotetrahedral-2a
TS1
TS2
TS3
MECP1
MECP2
S
S
T
S
T
T
8717.618927
8717.619329
8717.617610
8717.578526
8717.608959
8717.613271
8717.609981
8717.613556
0.3
0.0
1.1
25.6
6.5
3.8
8717.245909
8717.246368
8717.244651
8717.205819
8717.236599
8717.240309
0.3
0.0
1.1
25.4
6.2
3.8
5.9
3.6
(32 mg, 0.125 mmol) was dissolved and solution of NaОН (40 mg,
1.0 mmol) in EtOH (3 mL) was added to the prepared mixture at
stirring (23e25 ꢀC, 5 min). To a resulting solution of sodium thio-
selenophosphinate, NiCl2$6H2O (119 mg, 0.5 mmol) in EtOH
(10 mL) was added. The mixture was stirred for 5 min at 23e25 ꢀC,
diluted with water (30 mL) and extracted with CH2Cl2 (1 ꢂ 20 mL).
The organic layer was washed with water (2 ꢂ 10 mL), dried over
Na2SO4 and evaporated in vacuum. The solid obtained was dis-
solved in CH2Cl2 (5 mL) and the solution was layered with hexane
(20 mL) to afford complexes 2aec.
Nickel(II) bis(2-furan-2-ylethyl)thioselenophosphinate (2c)
Dark-green crystals, dec. > 130 ꢀC (CH2Cl2/hexane). Yield:
250 mg (69%). Anal. Calcd for C24H28NiO4P2S2Se2 (723.17): С, 39.86;
Н, 3.90. Found: С, 39.71; Н, 4.02. 1H NMR (400.13 MHz, CDCl3):
d
¼ 2.18e2.27 (m, 8Н, СН2Р), 2.80e2.90 (m, 8Н, CH2Fur), 6.03e7.29
(m, 12Н, Fur). 31P NMR (161.98 MHz, CDCl3):
1JPSe ¼ 450 Hz). 77Se NMR (76.31 MHz, CDCl3):
1JPSe ¼ 450 Hz).
d
¼ 72.05 (s,
¼ ꢁ340 (d,
d
X-ray crystallography
The X-ray quality single crystals of 2c were obtained by layering
of its CH2Cl2 solutions with hexane at room temperature. Data were
Characterization data for complexes 2aec
collected using the
diffractometer with graphite monochromated Mo-Ka radiation
with
¼ 0.71073 Å, and corrected for absorption using the multi-
u scans on a Bruker Kappa Apex II CCD
Nickel(II) diphenylthioselenophosphinate (2a)
Dark-green crystals, mp 223e225 ꢀC (CH2Cl2/hexane). Yield:
240 mg (74%). Anal. Calcd for C24H20NiP2S2Se2 (651.11): С, 44.27; Н,
3.10. Found: С, 44.20; Н, 3.15. 1H NMR (400.13 MHz, CDCl3):
l
scan method. The structure was solved using Patterson Methods,
followed by a Tangent Expansion (ShelXS). Non-hydrogen atoms
were refined anisotropically using SHELXTL97 [29]. Hydrogen
atoms were included at geometrically calculated positions during
the refinement using the riding model. The restrictions (equality of
parameters for atoms of one position) were used with the refine-
ment, in the other variants the refinement led to the poorer results.
Crystal data for 2c: C24H28NiO4P2S2Se2, Mr ¼ 723.15, triclinic,
d
¼ 7.46e7.55 (m, 12H, Ph), 7.76e7.82 (m, 8Н, Ph). 31P NMR
(161.98 MHz, CDCl3):
unavailable due to the poor solubility.
d
¼ 56.44. The 77Se NMR spectrum of 2a was
Nickel(II) bis(2-phenethyl)thioselenophosphinate (2b)
Dark-green crystals, mp 133e140 ꢀC (CH2Cl2/hexane). Yield:
310 mg (81%). Anal. Calcd for C32H36NiP2S2Se2 (763.32): С, 50.35; Н,
4.75. Found: С, 50.24; Н, 4.91. 1H NMR (400.13 MHz, CDCl3):
space group P-1,
c ¼ 15.0548(11) Å,
a
¼
8.7352(6) Å,
b
¼
11.5844(8) Å,
g
a
¼ 71.764(2)ꢀ,
b
¼ 81.602(3)ꢀ,
¼ 78.834(2)ꢀ,
1413.54(17) Å3,
Z
¼
2, dcalc
¼
1.699 g/cmꢁ3
, m(Mo-
d
¼ 2.29e2.36 (m, 8Н, СН2Р), 3.22e3.29 (m, 8Н, CH2Ph), 7.23e7.34
V
¼
(m, 20Н, Ph). 31P NMR (161.98 MHz, CDCl3):
1JPSe ¼ 458 Hz). 77Se NMR (76.31 MHz, CDCl3):
1JPSe ¼ 458 Hz).
d
¼ 73.73 (s,
¼ ꢁ346 (d,
Ka) ¼ 3.551 mme1
,
qmax ¼ 30.0ꢀ, measured/independent reflections
d
22,946/7879 (Rint ¼ 0.0335), data/restraints/parameters: 7879/0/
318, R indices: R1 ¼ 0.0376 [5080 I > 2
s
(I)], wR2 (all data) ¼ 0.1293,
GOF on F2 ¼ 1.012.
Acknowledgments
This work was supported by the President of the Russian
Federation (program for the support of leading scientific schools,
grant NSh-156.2014.3). The authors are also grateful to Victor I.
Mamatyuk for performing VT 31P NMR study of complex 2a.
Appendix A. Supplementary material
CCDC 855044 contains the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
Appendix B. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jorganchem.2014.06.013.
Fig. 4. VT 31P NMR spectra of complex 2a in CD2Cl2 solution.

156
A.V. Artem'ev et al. / Journal of Organometallic Chemistry 768 (2014) 151e156
[11] Y.-Q. Jiao, G.-W. Lu, K. Zhao, Y. Chen, J.-H. Lan, C.-J. Shao, Wang, J. Mol. Struct.
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