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)
%0 Journal Article
%1 Scheiring.2000
%A Scheiring, T.
%A Kaim, W.
%A Fiedler, J.
%D 2000
%J Journal of Organometallic Chemistry
%K acetyl bipyridine complex complex;geometrical crystal electronic manganese mol rhenium structure
%N 1
%P 136--141
%R 10.1016/S0022-328X(99)00691-9
%T Geometrical and electronic structures of the acetyl complex Re(bpy)(CO)3(COCH3) and of M(bpy)(CO)4(OTf), M = Mn, Re
%V 598
%X 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)
@article{Scheiring.2000,
abstract = {The compd. fac-Re(bpy)(CO)3(COCH3) (1) (bpy = 2,2'-bipyridine) with three different kinds of \textgreek{p}-acceptor ligands coordinated to rhenium(I) has been investigated by IR spectroelectrochem. to reveal the occupation of the \textgreek{p}*(bpy) MO on one-electron redn. to 1.bul.- with negligible participation of the \textgreek{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/\textgreek{p}*(bpy) and dxy/\textgreek{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)]},
added-at = {2022-06-15T11:26:56.000+0200},
author = {Scheiring, T. and Kaim, W. and Fiedler, J.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/294daffe474023bc42a2cc8f3dc99fb48/huebleriac},
doi = {10.1016/S0022-328X(99)00691-9},
interhash = {c258524a7d18118fdd5e3df4f27e3d93},
intrahash = {94daffe474023bc42a2cc8f3dc99fb48},
journal = {Journal of Organometallic Chemistry},
keywords = {acetyl bipyridine complex complex;geometrical crystal electronic manganese mol rhenium structure},
number = 1,
pages = {136--141},
timestamp = {2022-06-15T09:26:56.000+0200},
title = {Geometrical and electronic structures of the acetyl complex Re(bpy)(CO)3(COCH3) and of [M(bpy)(CO)4](OTf), M = Mn, Re},
volume = 598,
year = 2000
}