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Synthesis, Structure, and Solution Dynamics of Co₄(CO)₈(dmpe)(mu₄-PPh)₂Schulman, Cheryl Lutins 05 1900 (has links)
Reaction of the tetracobalt cluster Co4(CO)10(t 4-PPh)2 with 1,2-bis(dimethylphosphino)ethane
(dmpe) affords the bis-substituted cluster Co4(CO)8(dmpe)(t 4-PPh)2. The bidentate dmpe ligand is
shown to bind to the cluster in a chelating fashion by IR, NMR, and X-ray diffractions analyses.
The fluxional nature of the ancillary carbonyl groups has been studied by variable temperature 13C
NMR measurements which reveal two distinct carbonyl scrambling pathways. The stability of the
phosphine-ligated cluster has been examined using in situ Cylindrical Internal Reflection (CIR)
Spectroscopy. The effect of the dmpe ligand on the cluster polyhedron will be discussed with
respect to the observed crystallographic and spectroscopic results
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