precipitate formed. After stirring for 12 h all volatile components
were removed in vacuum. The residual brown solid was suspended
in 40 mL of boiling THF and the hot suspension filtered through
a glass fibre filter. After a few days at room temperature, deep red
crystals of 4·3THFhad formed. The mother liquor was decanted
and combined with the rest of the brown residue. This extraction
procedure was repeated three times to yield 1.9 g of pure 4·THF.
NMR (saturated solution in [D8]THF, ppm): 1H NMR: d = 7.46,
7.27, 7.12, 7.04, 6.47, 6.18, 6.11, 5.96, 5.76 (m, C6H4 and C6H5),
3.61, 1.76 (C4H8O); NH not identified and possibly overlapped;
31P NMR: two multiplets (AAꢀBBꢀ spin system) d(PA) = 50.5,
6 O. Ku¨hl, S. Blaurock, J. Sieler and E. Hey-Hawkins, Polyhedron, 2001,
20, 2171.
7 T. Shibata, H. Tsuruta, H. Danjo and T. Imamoto, J. Mol. Catal. A,
2003, 196, 117; and ref. cited therein.
8 Review: M. Rodriguez, I. Zubiri and J. D. Woollins, Comments Inorg.
Chem., 2003, 24, 189–252; and ref. cited therein.
9 J. Ansell and M. Wills, Chem. Soc. Rev., 2002, 31, 259.
10 (a) O. Ku¨hl, T. Koch, F. B. Somoza Jr, P. C. Junk, E. Hey-Hawkins, D.
Plat and M. S. Eisen, J. Organomet. Chem., 2000, 604, 116; (b) T. G.
Wetzel, S. Dehnen and P. W. Roesky, Angew. Chem., Int. Ed., 1999,
111, 1155; (c) W. Schirmer, U. Flo¨rke and H.-J. Haupt, Z. Anorg. Allg.
Chem., 1987, 545, 83.
11 S. Breeden, D. J. Cole-Hamilton, D. F. Foster, G. J. Schwarz and M.
Wills, Angew. Chem., Int. Ed., 2000, 39, 4106.
12 F. Majoumo-Mbe, P. Lo¨nnecke and E. Hey-Hawkins, Organometallics,
2005, 24, 5287.
ꢀ
ꢀ
d(PB) = 13.8; JAA = 153.0(2), JAB = −73.0(4), JAB = 41.6(1),
JBB = 57.6(2) Hz; 13C NMR: Due to the low solubility no
ꢀ
13 F. Majoumo Mbe, P. Lo¨nnecke, E. Butovsky, D. Shpasser, M. S. Eisen
and E. Hey-Hawkins, J. Mol. Catal. A, 2005, 240, 91.
14 F. Majoumo-Mbe, P. Lo¨nnecke, V. Volkis, M. Sharma, M. S. Eisen and
E. Hey-Hawkins, J. Organomet. Chem., 2008, accepted.
15 O. Ku¨hl, P. C. Junk and E. Hey-Hawkins, Z. Anorg. Allg. Chem., 2000,
626, 1591.
informative spectrum could be obtained. IR (KBr, cm−1): 3347w,
3052m, 2965w, 2867w, 1588m, 1573w, 1494vs, 1481m, 1454m,
1435s, 1387w, 1294vs, 1228w, 1182w, 1157w, 1121s, 1095vs, 1057m,
1027w, 962m, 908w, 808m, 740s, 694vs, 641w, 533vs, 511vs, 493w,
465m.
16 O. Ku¨hl, S. Blaurock, J. Sieler and E. Hey-Hawkins, Polyhedron, 2001,
20, 111.
17 T. Q. Ly, A. M. Z. Slawin and J. D. Woollins, J. Chem. Soc., Dalton
Trans., 1997, 1611.
Structure determination
18 F. Majoumo, P. Lo¨nnecke, O. Ku¨hl and E. Hey-Hawkins, Z. Anorg.
Allg. Chem., 2004, 630, 305.
19 W. Schirmer, U. Flo¨rke and H.-J. Haupt, Z. Anorg. Allg. Chem., 1987,
545, 83.
20 (a) D. Benito-Garagorri, E. Becker, J. Wiedermann, W. Lackner, M.
Pollak, K. Mereiter, J. Kisala and K. Kirchner, Organometallics, 2006,
25, 1900; (b) D. Benito-Garagorri, V. Bocokic´, K. Mereiter and K.
Kirchner, Organometallics, 2006, 25, 3823.
21 F. Majoumo-Mbe, P. Lo¨nnecke and E. Hey-Hawkins, Organometallics,
2005, 24, 5287.
Data were collected on a Siemens CCD diffractometer (SMART)
using MoKa radiation (k = 71.073 pm) and x-scan rotation. Data
reduction was performed with SAINT including the program
SADABS for empirical absorption correction. The structure was
solved by direct methods and the refinement of all non-hydrogen
atoms was performed with SHELXL-97. For the free ligands all
hydrogen atoms were found (1) and only the positions of some
poorly defined methyl (2) and/or solvent hydrogen atoms (2b) were
calculated. For all other compounds, H atoms attached to carbon
were mainly calculated on idealised positions. Due to divergent
final refinement cycles in 3, three poorly defined THF solvent
molecules were removed by using the program SQUEEZE.41
Structure figures were generated with ORTEP.42 CCDC 671847
(1), 671845 (2), 671849 (2b), 671846 (3) and 671848 (4) contain the
supplementary crystallographic data for this paper.‡
22 D. Fenske, B. Maczek and K. Maczek, Z. Anorg. Allg. Chem., 1997,
623, 1113.
23 S. A. Bell, S. J. Geib and T. Y. Meyer, Inorg. Chem., 1999, 38, 2524.
24 SpinWorks, Version 2.3 by Kirk Marat, University of Manitoba.
¯
25 Triclinic, space group P1, formula: C60H50N4Ni2P4·3THF, a = 1229
pm, b = 1267 pm, c = 2252 pm, a = 85.7◦, b = 82.7◦, c = 66.2◦.
26 (a) R. A. Jones, A. L. Stuart, J. L. Atwood, W. E. Hunter and R. D.
Rogers, Organometallics, 1982, 1, 1721; (b) B. L. Barnett and C. Kru¨ger,
Cryst. Struct. Commun., 1973, 2, 85; (c) C. E. Kriley, C. J. Woolley,
M. K. Krepps, E. M. Popa, P. E. Fanwick and I. P. Rothwell, Inorg.
Chim. Acta, 2000, 300, 200.
Acknowledgements
27 (a) R. A. Jones, A. L. Stuart, J. L. Atwood and W. E. Hunter,
Organometallics, 1983, 2, 874; (b) A. M. Arif, R. A. Jones and S. T.
Schwab, J. Coord. Chem., 1987, 16, 51; (c) R. A. Jones, A. L. Stuart,
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28 R. A. Jones, N. C. Norman, M. H. Seeberger, J. L. Atwood and W. E.
Hunter, Organometallics, 1983, 2, 1629.
We gratefully acknowledge support from the “South-Eastern
Europe Stability Pact” (DAAD Programme, contract no.
A/05/08166).
29 E. Simon-Manso and C. P. Kubiak, Inorg. Chem. Commun., 2003, 6,
1096.
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