c = 17.070(7) A, a = 111.295(6), b = 104.846(7), g = 99.201(18)1,
V = 2425.6(13) A3, T = 123(1) K, Z = 2, m(CuKa) = 20.615 mmꢀ1
,
10 270 reflections measured, 6061 unique (Rint = 0.027) which were
used in all calculations. The final R1 [I 4 2s(I)] was 0.0301. The low
completeness and relatively low resolution of the data set affect
adversely the geometric parameters (see ESIz). Crystal data for 4ꢃ
ꢀ
C7H8: C39H18As2O20P4W4, M = 1815.61, triclinic, space group P1,
a = 12.2685(5), b = 12.4386(5), c = 18.7689(7) A, a = 96.500(3),
b = 102.035(4), g = 115.791(4)1, V = 2453.6(2) A3, T = 123(1) K,
Z = 2, m(CuKa) = 20.288 mmꢀ1, 13 743 reflections measured, 7523
unique (Rint = 0.0401) which were used in all calculations. The final
R1 [I 4 2s(I)] was 0.0390.
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Coordination in Phosphorus Chemistry, Georg Thieme Verlag,
Stuttgart, 1990.
Scheme 2 Proposed reaction mechanism for the formation of 3 and 4.
primary diphosphines to generate the 1,2,3-triphosphole and
2-arsa-1,3-diphosphole derivatives as intermediates that sub-
sequently react to give novel polycyclic phosphorus and
arsenic containing cage compounds. The found pentelidene-
induced aggregation process is different from the previously
reported metal-mediated dehydrocoupling leading both to
group 15 element-rich cage compounds.14
5 A. Dransfeld, L. Nyula
´
1998, 37, 4413; L. Nyula
szi and P. v. R. Schleyer, Inorg. Chem.,
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´
´
¨
M. Regitz and P. v. R. Schleyer, New J. Chem., 1998, 22, 651;
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6 C. P. Butts, M. Green, T. N. Hooper, R. J. Kilby, J. E. McGrady,
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The authors thank the Deutsche Forschungsgemeinschaft
and the Fonds der Chemischen Industrie for financial
support.
7 F. Garcı
D. S. Wright, Angew. Chem., 2007, 119, 7973 (Angew. Chem., Int.
Ed., 2007, 46, 7827); F. Garcıa, R. J. Less, V. Naseri,
´
a, R. J. Less, V. Naseri, M. McPartlin, J. M. Rawson and
´
Notes and references
M. McPartlin, J. M. Rawson, M. S. Tomas and D. S. Wright,
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8 R. Kroos, PhD thesis, Universitat Bielefeld, 1989; P. Jutzi and
¨
R. Kroos, J. Organomet. Chem., 1990, 390, 317.
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y 3: A solution of 1,2-diphosphinobenzene (62 mg, 0.44 mmol) was
added to a solution of [Cp*P{W(CO)5}2] (1) (175 mg, 0.22 mmol) in
toluene (20 cm3) at room temperature. The blue colour of 1 turns to
orange after 16 hours stirring at room temperature. The reaction
mixture was concentrated to approximately 2 cm3 and layered with
5 cm3 hexane to give pale yellow crystals of 3ꢃ1.5CH2Cl2 (27 mg, 8%).
MS (EI, 70 eV) m/z 1636 (M+, 2%), 1312 (M+-W(CO)5, 2). IR (KBr)
n
max/cmꢀ1 2068m, 1998vs, 1946s (CO). 4: A solution of 1,2-diphos-
phinobenzene (58 mg, 0.41 mmol) was added to a solution of
[Cp*As{W(CO)5}2] (2) (172 mg, 0.20 mmol) in toluene (20 cm3) at
ꢀ78 1C. After the reaction mixture was allowed to slowly warm up to
room temperature and stirred for two days, the colour of the reaction
mixture turned to brown. The reaction mixture was concentrated to
approximately 5 cm3 and layered with 5 cm3 hexane to give pale yellow
crystals of 4ꢃC6H5CH3 (38 mg, 11%). 1H NMR dH (400 MHz; CD2Cl2;
Me4Si) 4.77 (1 H, m, As–H), 6.94 (1 H, dm, JHP 321 Hz, P–H), 8.10
(8 H, m, C6H4). 31P{1H} NMR dP (161 MHz; CD2Cl2; Me4Si) ꢀ31.5
(1 P, ddd, JPP 4, JPP 13, JPP 17, P4), 13.4 (1 P, ddd, JPP 3, JPP 12,
JPP 13, P1), 41.1 (1 P, ddd, JPP = 229, JPP 4, JPP 12, P3), 61.3 (1 P, ddd,
JPP 229, JPP 4, JPP 17, P2). IR (KBr) nmax/cmꢀ1 2068s, 1998s, 1920vs
(CO). MS (EI, 70 eV) m/z 1723 (M+, 2%), 1695 (M+ ꢀ CO, 2), 862
(1/2ꢃM+, 42).
2493; for reviews see: B. P. Johnson, G. Bala
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´
zs and M. Scheer,
´
12 M. Scheer, D. Himmel, B. P. Johnson, C. Kuntz and M. Schiffer,
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16 Synthetic details and analytical data for 5 and 6 are given
in ESIz.
¨
z Crystal data for 3ꢃCH2Cl2: C33H12O20Cl2P6W4, M = 1720.51,
ꢀ
triclinic, space group P1
a = 11.547(3), b = 14.237(3),
ꢂc
This journal is The Royal Society of Chemistry 2009
Chem. Commun., 2009, 1745–1747 | 1747