Geometrical and electronic structures of the acetyl complex Re(bpy)(CO)3(COCH3) and of M(bpy)(CO)4(OTf), M = Mn, Re
, , und .
Journal of Organometallic Chemistry 598 (1): 136--141 (2000)

The compd. fac-Re(bpy)(CO)3(COCH3) (1) (bpy = 2,2'-bipyridine) with three different kinds of p-acceptor ligands coordinated to rhenium(I) has been investigated by IR spectroelectrochem. to reveal the occupation of the p*(bpy) MO on one-electron redn. to 1.bul.- with negligible participation of the p-accepting acetyl group. The results are discussed in relation to the spectroscopy (NMR, IR) and the crystal structure anal. of the neutral complex 1, which reveals a short C-O(acetyl) (1.157(12) \AA) and a long Re-C(acetyl) bond (2.245(12) \AA) and an orientation of the Re-C(O)CH3 plane parallel to the C2 axis of the coordinated bpy. The result is an orthogonal arrangement of dxz/p*(bpy) and dxy/p*(acetyl) orbitals. This situation stands in distinct contrast to the structure reported for the complex salt Re(L)(CO)3(COCH3)(PPN) (PPN+ = bis(triphenylphosphoranylidene)ammonium) with a cyclometalated 2-phenylpyridine ligand L. The crystal structures of the related complexes M(bpy)(CO)4(OTf), M = Re and Mn, were detd. for comparison. on SciFinder(R)
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