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Title: New rhenium(I) compounds containing the donor-acceptor diphosphine ligands 2-(ferrocenylidene)-4,5-bis(diphenylphosphino)4-cyclopenten-1,3-dione (fbpcd) and 2-(3-ferrocenylprop-2-ynylidene)-4,5-bis(diphenylphosphino)4-cyclopenten-1,3-dione (fpbpcd): Electrochemical behavior, MO properties, and X-ray diffraction structure of fac-BrRe(CO)(3)(fpbpcd)

Journal Article · · Polyhedron

Displacement of the labile THF molecules in BrRe(CO){sub 3}(THF){sub 2} (1) by the diphosphine ligands 2-(ferrocenylidene)-4,5-bis(diphenylphosphino)4-cyclopenten-1,3-dione (fbpcd) and 2-(3-ferrocenylprop-2-ynylidene)-4,5-bis(diphenylphosphino)4-cyclopenten- 1,3-dione (fpbpcd) yields the mononuclear compounds fac-BrRe(CO){sub 3}(fbpcd) (2) and fac-BrRe(CO){sub 3}(fpbpcd) (3), respectively. The new ligand fpbpcd ligand has been synthesized from 3-ferrocenylpropynal and the parent diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) through a Knoevenagel condensation. 2 and 3 have been isolated and fully characterized by IR and NMR spectroscopies ({sup 1}H and {sup 31}P), ESI mass spectrometry, and X-ray diffraction analysis in the case of 3. The electrochemical properties of compounds 2 and 3 have been examined by cyclic voltammetry, and the nature of the HOMO and LUMO levels in these systems has been confirmed by MO calculations at the extended Hueckel level. The redox and MO data are discussed relative to the redox and orbital properties of related functionalized diphosphines based on the bpcd platform.

Research Organization:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
ORNL other overhead
DOE Contract Number:
DE-AC05-00OR22725
OSTI ID:
1045247
Journal Information:
Polyhedron, Vol. 28, Issue 13; ISSN 0277-5387
Country of Publication:
United States
Language:
English