Mendeleev Commun., 2012, 22, 187–188
approximately 0.02 Å shorter than the Co(1)–N(1) distance
P
P
P
P
[2.1614(9) Å]. The Co(1)–P(1) distance is 3.4840(5) Å. Note that
complex 2 is a rare example of cobalt ‘sandwich’ pyridylphos-
phine complexes. Hitherto, only few representatives of these
P
P
P
P
OH
P
P
P
+
HO P
1
2
complexes were prepared.
In conclusion, a novel straightforward one-pot microwave-
assisted preparation of tris(2-pyridyl)phosphine in a yield of up
to 53% from available 2-bromopyridine and red phosphorus in
A
B
Fragment of Pn
macromolecule
the superbasic KOH/DMSO (H O) suspension has been disclosed.
2
P
Thus, tris(2-pyridyl)phosphine is now gaining a position of an
available phosphine ligand. Special ligation properties of this
phosphine have been confirmed by the synthesis of complex
A
+
P
1
–
Br
N
Br
P
N
[
Co(2-Py P) ]Cl ∙8H O in which the two phosphorus atoms do
3 2 2 2
Scheme 2
not participate in coordination with the metal, while six pyridine
nitrogen atoms are involved in the formation of a rare cage
complex structure.
C(4*)
C(3*)
P(1)
C(4)
C(5*)
N(1*)
This work was supported by the Russian Foundation for Basic
Research (grant no. 11-03-00286).
C(5)
N(1)
C(3)
C(9)
C(10)
N(2)
C(2*)
C(8)
C(7)
Online Supplementary Materials
Supplementary data (details of H, 13C and 31P NMR spectra
of phosphine 1 and crystallographic data for complex 2) asso-
ciated with this article can be found in the online version at
doi:10.1016/j.mencom.2012.06.004.
1
C(1*)
C(2)
C(6)
Co(1)
C(1)
C(1')
C(6')
C(2')
C(3')
N(1')
N(2')
N(1'')
C(1'')
C(7')
References
C(5')
C(2'')
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C(10')
C(8')
C(9') P(1')
C(5'')
C(4')
C(3'')
C(4'')
2
+
Figure 1 X-ray structure for the cation [Co(2-Py P) ] in complex 2.
Selected bond lengths (Å): Co(1)–P(1) 3.4840(5), Co(1)–N(1) 2.1614(9),
Co(1)–N(2) 2.145(1), P(1)–C(10) 1.839(1), P(1)–C(5) 1.840(1).
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2
3
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1
4
2
2
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‡
Bis[tris(2-pyridyl)phosphine]cobalt(ii) dichloride octahydrate 2. A mix-
5
6
ture of tris(2-pyridyl)phosphine 1 (530 mg, 2.0 mmol) and CoCl ∙6H O
2
2
(
3
238 mg, 1.0 mmol) in 95% EtOH (15 ml) was stirred at 45–50°C for
0 min to yield a red suspension. The latter was cooled to room tempe-
rature and the solid was filtered off. The resulting orange solution was
allowed to stand overnight at 5–8°C. The complex precipitated was filtered
off, washed with EtOH–Et O (1:2) and dried in vacuo (1 Torr) to give
orange crystals.Yield, 0.63 g (78%), mp 137–139°C (decomp.). IR (film,
n/cm ): 3437, 3105, 3083, 3023, 2924, 2856, 1637, 1602, 1495, 1453,
7
8
(a) E. Drent, P. Arnoldy and P. H. M. Budzelaar, J. Organomet. Chem.,
2
1
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–1
1
5
393, 1263, 1210, 1179, 1127, 1067, 1029, 1005, 944, 908, 855, 746, 697,
73, 512, 483. 31P NMR (DMSO-d ) d: –1.72. Found (%): C, 44.67;
6
H, 5.11; N, 10.39; P, 7.59. Calc. for C H Cl CoN O P (%): C, 44.79;
30
40
2
6
8 2
H, 5.01; N, 10.45; P, 7.70.
Crystal data for 2. Crystals of 2 (C H CoN P ∙8H O∙2Cl, M = 804.45)
10 A. M. Kluwer, I. Ahmad and J. N. H. Reek, Tetrahedron Lett., 2007, 48,
2999.
§
30
24
6
2
2
are monoclinic, space group C /m, a = 12.187(1), b = 13.449 (1) and c =
11 (a) B. A. Trofimov and N. K. Gusarova, Mendeleev Commun., 2009, 19,
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2
3
–3
=
11.455(1) Å, b = 101.505(1)°, V = 1839.8(3) Å , Z = 2, d = 1.45 g cm ,
calc
–1
m(MoKa) = 0.754 mm , 2q = 55.04°. X-ray diffraction analysis was
max
1
2 K. R. Adam, P. A. Anderson, T. Astley, I. M. Atkinson, J. M. Charnock,
C. D. Garner, J. M. Gulbis, T. W. Hambley, M. A. Hitchman, F. R. Keene
and E. R. T. Tiekink, J. Chem. Soc., Dalton Trans., 1997, 519.
performed on a Bruker SMART APEX-II CCD diffractometer at 173 K
[
l(MoKa) = 0.71073 Å, w-scans]. 6358 reflections were measured, from
which 2112 reflections were independent, R = 0.023 for 1990 reflections
1
1
3 G. M. Sheldrick, SHELXS-97, SHELXL-97, Programs for the Solution and
Refinement of Crystal Structures, University of Göttingen, Germany, 1997.
with [F > 4s(F )]. The structure was solved by direct methods and refined
0
0
by a full matrix least-squares anisotropic procedure using SHELXTL97
programs.13
CCDC 863027 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.
For details, see ‘Notice to Authors’, Mendeleev Commun., Issue 1, 2012.
Received: 6th February 2012; Com. 12/3873
188 –
–