Synthesis and the structure of the triphenylphosphine complex of o-nickelacarborane, 3,3-(PPh3)2-3,1,2-NiC2B9H11

Article abstract of DOI:10.1023/A:1015098628735

The reaction of bis(o-dicarbollyl)nickel(IV) with PPh₃ in EtOH gave rise to the complex 3,3-(PPh₃)₂-3,1,2-NiC₂B₉H₁₁ (2) whose structure was established by X-ray diffraction analysis.

Full text of DOI:10.1023/A:1015098628735

2248
Russian Chemical Bulletin, International Edition, Vol. 50, No. 11, pp. 2248—2250, November, 2001
Synthesis and the structure of the triphenylphosphine complex
of o-nickelacarborane, 3,3-(PPh3)2-3,1,2-NiC2B9H11
A. A. Erdman,a Z. P. Zubreichuk,b« V. A. Knizhnikov,b A. A. Maier,b
G. G. Aleksandrov,c S. E. Nefedov,c« and I. L. Eremenkoc«
aInstitute of Chemistry of New Materials, National Academy of Sciences of Belarus,
36 Staroborisovskii trakt, 220141 Minsk, Belarus.
Fax: (+37517) 264 7007. E-mail: slavol@nx.ichnm
bInstitute of Physical Organic Chemistry, National Academy of Sciences of Belarus,
13 ul. Surganova, 220072 Minsk, Belarus.
Fax: (+37517) 284 1679. E-mail: maier@ifoch.bas-net.by
cN. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
31 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: (095) 954 1279. E-mail: ilerem@igic.ras.ru
The reaction of bis(o-dicarbollyl)nickel(IV) with PPh3 in EtOH gave rise to the complex
3,3-(PPh3)2-3,1,2-NiC2B9H11 (2) whose structure was established by X-ray diffraction
analysis.
Key words: metallocarboranes, X-ray diffraction analysis.
Previously,1—4 it has been found that nickelacarborane
It should be noted that refluxing of structurally char-
acterized complex 2 in benzene or ethanol did not afford
red products, unlike the complex to which structure 2
has been assigned previously5,6 and which has been
prepared by the reaction of (triphenylphosphine)nickel
chloride with thallium dicarbollide.5,6
complexes with coordinated nitrogen-containing ligands
of the general formula L2NiC2B9H11, where L2 is 2,2´-bi-
pyridyl (bipy) or 1,10-phenanthroline (phen), can be
prepared in preparative yields by the reactions of salts of
bis(o-dicarbollyl)nickel(III) or neutral bis(o-dicarbol-
lyl)nickel(IV) (1) with the corresponding ligands in etha-
nol. The structures of the resulting complexes were
established by X-ray diffraction analysis.3
Experimental
The IR spectra were recorded on a Nicolet Protegee-460
IR Fourier spectrophotometer (USA) in KBr pellets. The mass
In the present study, we synthesized the bis-
triphenylphosphine complex of o-nickelacarborane,
3,3-(PPh3)2-3,1,2-NiC2B9H11 (2), by the reaction of
triphenylphosphine with complex 1 in ethanol. The
highest yield of complex 2 (41%) was obtained using the
reagent ratio PPh3 : 1 = 3 : 1. An increase in the reagent
ratio to 4 : 1 did not lead to an increase in the yield,
whereas the reaction with the use of the stoichiometric
ratio (2 : 1) afforded complex 2 in lower yield (28—29%).
The reaction proceeded slowly even at room tempera-
ture. At the temperature of the boiling solvent, the
reaction was completed in 2 h.
Complex 2 was obtained as an olive-green crystalline
compound, which did not melt up to 250 °C. According
to the X-ray diffraction data (Fig. 1, Tables 1 and 2), the
NiII atom in complex 2 is coordinated by two phospho-
rus atoms of the triphenylphosphine ligands (Ni—P,
2.238(2) and 2.216(2) Å) and by the open face of
the carbollyl fragment (Ni(1)—C(1), 2.096(7) Å;
Ni(1)—C(2), 2.141(5) Å; C(1)—C(2), 1.620(8) Å;
Ni(1)—B(1), 2.095(7) Å; Ni(1)—B(2), 2.176(7) Å;
Ni(1)—B(3), 2.159(6) Å). All distances in the carbollyl
dianion have values typical of compounds of this type
(Table 2).
Table 1. Crystallographic parameters of complex 2
Parameter
Characteristic
C38H41B9NiP2
Molecular formula
Molecular weight
Space group
a/Å
b/Å
c/Å
α/deg
β/deg
γ/deg
V/Å3
715.65
P1
–
10.836(2)
11.571(2)
16.620(3)
84.652(4)
76.016(4)
64.211(5)
1820.6(5)
2
1.305
6.490
1.26—30.11
12696
Z
–3
ρ
calc/g cm
–1
µ/cm
θ/2θ Scan range
Number of measured reflections
Number of reflections with I > 2σ
9544
Number of parameters in the refinement 615
R1 (I > 2σ(I ))
wR2
0.0709
0.1321
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2146—2148, November, 2001.
1066-5285/01/5011-2248 $25.00 © 2001 Plenum Publishing Corporation

Structure of 3,3-(PPh3)2-3,1,2-NiC2B9H11
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 11, November, 2001 2249
C(24)
C(23)
C(6)
C(5)
C(25)
C(7)
C(11)
C(22)
C(37)
C(4)
C(38)
C(26)
C(33)
C(21)
C(36)
C(3)
C(9)
C(12)
C(8)
C(35)
C(34)
C(13)
C(14)
C(27)
C(16)
C(32)
P(1)
P(2)
C(17)
C(18)
C(31)
C(15)
C(20)
C(28)
Ni(1)
C(29)
C(30)
B(3)
C(19)
B(2)
C(2)
B(1)
C(1)
B(6)
B(4)
B(7)
B(8)
B(5)
B(9)
Fig. 1. Structure of complex 2.
Table 2. Selected bond lengths (d) and bond angles (ω) in complex 2
Bond
d/Å
Angle
ω/deg
Angle
ω/deg
Angle
ω/deg
Ni(1)—C(1) 2.096(7)
Ni(1)—C(2) 2.141(5)
Ni(1)—B(2) 2.176(7)
C(1)—Ni(1)—B(1)
B(1)—Ni(1)—C(2)
B(1)—Ni(1)—B(3)
C(1)—Ni(1)—B(2)
C(2)—Ni(1)—B(2)
C(1)—Ni(1)—P(2)
C(2)—Ni(1)—P(2)
B(2)—Ni(1)—P(2)
B(1)—Ni(1)—P(1)
B(3)—Ni(1)—P(1)
P(2)—Ni(1)—P(1)
79.9(3)
80.7(2)
51.1(2)
45.3(3)
79.4(2)
161.9(2)
143.4(2)
116.6(2)
174.5(2)
131.3(2)
97.64(6)
C(1)—B(7)—B(8)
C(1)—B(7)—B(9)
C(2)—B(8)—B(9)
C(2)—B(8)—B(7)
C(2)—C(1)—B(6)
C(2)—C(1)—B(7)
B(6)—C(1)—B(7)
B(2)—C(1)—Ni(1)
B(7)—C(1)—Ni(1)
B(3)—C(2)—B(8)
B(3)—C(2)—B(7)
B(8)—C(2)—B(7)
C(1)—C(2)—Ni(1)
B(7)—C(2)—Ni(1)
C(1)—Ni(1)—C(2)
C(1)—Ni(1)—B(3)
C(2)—Ni(1)—B(3)
B(1)—Ni(1)—B(2)
B(3)—Ni(1)—B(2)
B(1)—Ni(1)—P(2)
B(3)—Ni(1)—P(2)
C(1)—Ni(1)—P(1)
C(2)—Ni(1)—P(1)
B(2)—Ni(1)—P(1)
C(3)—P(1)—Ni(1)
C(9)—P(1)—Ni(1)
104.7(5)
103.8(5)
104.4(4)
58.7(4)
110.7(5)
61.5(4)
61.1(4)
69.9(3)
127.2(4)
64.2(4)
115.6(5)
61.6(4)
66.1(3)
125.2(4)
44.9(2)
78.3(2)
44.6(2)
49.8(2)
84.5(2)
86.1(2)
101.7(2)
95.7(2)
98.4(2)
124.8(2)
115.9(2)
111.2(2)
B(5)—B(1)—Ni(1)
B(3)—B(1)—Ni(1)
C(1)—B(2)—B(6)
C(1)—B(2)—B(1)
B(5)—B(2)—Ni(1)
B(1)—B(2)—Ni(1)
C(2)—B(3)—B(8)
C(2)—B(3)—Ni(1)
B(8)—B(3)—Ni(1)
C(1)—B(6)—B(2)
B(2)—B(6)—B(5)
C(1)—B(6)—B(9)
C(2)—B(7)—B(6)
C(2)—B(7)—B(8)
C(2)—B(7)—B(9)
C(2)—B(8)—B(4)
C(2)—B(8)—B(3)
C(2)—C(1)—B(2)
B(2)—C(1)—B(6)
B(2)—C(1)—B(7)
C(2)—C(1)—Ni(1)
B(6)—C(1)—Ni(1)
B(3)—C(2)—C(1)
C(1)—C(2)—B(8)
C(1)—C(2)—B(7)
B(3)—C(2)—Ni(1)
B(8)—C(2)—Ni(1)
120.1(4)
66.3(3)
60.5(4)
102.5(5)
117.6(4)
62.8(3)
60.6(4)
67.1(3)
122.5(4)
56.1(4)
59.4(4)
104.4(5)
105.1(5)
59.7(4)
104.0(5)
100.7(4)
55.2(3)
115.1(5)
63.4(4)
115.8(5)
69.0(3)
127.5(5)
111.4(5)
110.9(4)
62.3(4)
68.3(3)
126.7(4)
Ni(1)—P(1)
2.238(2)
P(1)—C(15) 1.833(6)
P(2)—C(33) 1.809(6)
P(2)—C(21) 1.851(6)
B(1)—B(3)
B(3)—C(2)
B(7)—C(1)
C(1)—C(2)
1.836(9)
1.632(8)
1.725(9)
1.620(8)
Ni(1)—B(1) 2.095(7)
Ni(1)—B(3) 2.159(6)
C(15)—P(1)—Ni(1) 113.4(2)
C(33)—P(2)—Ni(1) 114.5(2)
C(21)—P(2)—Ni(1) 119.7(2)
Ni(1)—P(2)
P(1)—C(3)
P(1)—C(9)
2.216(2)
1.810(5)
1.824(6)
B(4)—B(1)—Ni(1)
B(2)—B(1)—Ni(1)
C(1)—B(2)—B(5)
B(5)—B(2)—B(6)
C(1)—B(2)—Ni(1)
B(6)—B(2)—Ni(1)
C(2)—B(3)—B(4)
C(2)—B(3)—B(1)
B(4)—B(3)—Ni(1)
B(1)—B(3)—Ni(1)
C(1)—B(6)—B(5)
C(1)—B(6)—B(7)
C(2)—B(7)—C(1)
C(1)—B(7)—B(6)
119.1(4)
67.5(3)
105.0(5)
59.8(4)
64.8(3)
120.3(4)
106.5(5)
104.3(4)
117.9(4)
62.6(3)
101.4(5)
59.4(4)
56.2(3)
59.5(4)
P(2)—C(27) 1.840(6)
B(1)—B(2)
B(2)—C(1)
B(7)—C(2)
B(8)—C(2)
1.798(9)
1.648(10)
1.713(9)
1.732(8)
C(27)—P(2)—Ni(1) 114.9(2)
B(2)—B(1)—B(3) 106.6(5)

2250
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 11, November, 2001
Erdman et al.
spectra were obtained on a Varian MAT-311 spectrometer.
The UV spectra were measured on a Specord UV VIS
spectophotometer; the samples were prepared as 0.0001 M
solutions in ethanol. Bis(o-dicarbollyl)nickel(IV) (1) was pre-
pared according to a procedure described previously.7 The
reactions were carried out under an argon atmosphere.
Synthesis of 3,3´-bis(triphenylphosphino)-1,2-dicarba-3-
nickela-closo-dodecaborane(II) (2). A. A solution of triphenyl-
phosphine (0.78 g, 3 mmol) in a mixture of anhydrous ethanol
(20 mL) and dichloromethane (5 mL) was added to a solution
of bis(o-dicarbollyl)nickel(IV) (0.32 g, 1 mmol) in anhydrous
ethanol (30 mL). The reaction mixture was refluxed for 2 h
and then slowly cooled on an oil bath to 20 °C. The olive-
green crystals that precipitated were separated from the solu-
tion by decantation, washed with ethanol and hexane, and
dried in vacuo (0.1 Torr, 22 °C). Complex 2 was obtained in a
yield of 0.30 g (41.9%). Found (%): C, 63.00; H, 6.19;
Ni, 7.94. C38H41B9NiP2. Calculated (%): C, 63.77; H, 5.77;
Ni, 8.20. IR, ν/cm–1: 3060 s, 2560 s, 1590 w, 1575 w, 1313 w,
1190 m, 1165 m, 1128 m, 1091 m, 1030 w, 1000 w, 982 w,
References
1. N. A. Maier, A. A. Erdman, Z. P. Zubreichuk, V. P.
Prokopovich, and Yu. A. Ol´dekop, J. Organomet. Chem.,
1985, 292, 297.
2. A. A. Erdman, Z. P. Zubreichuk, N. A. Maier, and Yu. A.
Ol´dekop, Zh. Obshch. Khim., 1988, 38, 334 [J. Gen.
Chem. USSR, 1988, 38 (Engl. Transl.)].
3. A. A. Erdman, Z. P. Zubreichuk, V. P. Prokopovich, A. V.
Polyakov, A. I. Yanovsky, Yu. T. Struchkov, N. A. Maier,
and Yu. A. Ol´dekop, Koord. Khim., 1989, 15, 122 [Sov.
J. Coord. Chem., 1989, 15 (Engl. Transl.)].
4. A. A. Erdman, Z. P. Zubreichuk, N. A. Maier, I. A.
Shingel´, and Yu. A. Ol´dekop, Vests³ AN BSSR, Ser.
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5. S. B. Miller and M. F. Hawthorne, J. Chem. Soc., Chem.
Commun., 1976, 786.
6. R. E. King, S. B. Miller, C. B. Knobler, and M. F.
Hawthorne, Inorg. Chem., 1983, 22, 3548.
750 m, 725 m, 700 s, 545 s, 525 m, 515 m. MS, m/z, ion: 395,
7. M. F. Hawthorne, D. C. Young, T. D. Andrews, D. V.
Howe, R. L. Pilling, A. D. Pitts, M. Reintjes, L. F.
Warren, Jr., and P. A. Wegner, J. Am. Chem. Soc., 1968,
90, 879.
8. SMART (control) and SAINT (integration) Software, Ver-
sion 5.0, Bruker AXS Inc., Madison, WI, 1997.
9. G. M. Sheldrick, SADABS, Program for Scaling and Correc-
tion of Area Detector Data, University of Göttingen, 1997
(based on the method of R. H. Blessing, Acta Crystallogr., A,
1995, 51, 33).
10. G.M.Sheldrick, SHELXS 97, Program for the Solution
of Crystal Structures, University of Göttingen, Ger-
many, 1997.
11. G.M.Sheldrick, SHELXL 97, Program for the Refinement
of Crystal Structures, University of Göttingen, Ger-
many, 1997.
C20H25B9P+; 262, PPh3+; 192, C2H11B9Ni+; 134, C2B9H11
77, C6H5+; 58, Ni+. UV, nm: 212, 226, 263.
;
+
B. In another experiment, the above-described reaction
mixture was kept at ∼20 °C for 24 h. The yield of 2 was
0.29 g (40.5%).
X-ray diffraction analysis of complex 2. X-ray diffraction
analysis was performed in the Center of X-ray Diffraction
Studies (A. N. Nesmeyanov Institute of Organoelement Com-
pounds of the Russian Academy of Sciences) on a Bruker AXS
SMART 1000 diffractometer equipped with a CCD detector
(λMo radiation, graphite monochromator, 110 K, ω scanning
technique, the scan step was 0.3°, frames were exposed for
30 s, 2θmax = 60°) according to a standard procedure.8 The
semiempirical correction for absorption was applied.9 The
structure was solved by the direct methods using the SHELXS 97
program package10 and refined by the full-matrix least-squares
method with anisotropic thermal parameters (the positions of
the H atoms were fixed with UH = 0.08 Å2) using the
SHELXL 97 program package.11
Received September 7, 2001