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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)

Abstract

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.

Authors:
 [1];  [1]
  1. University of North Texas
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
ORNL other overhead
OSTI Identifier:
1045247
DOE Contract Number:  
DE-AC05-00OR22725
Resource Type:
Journal Article
Journal Name:
Polyhedron
Additional Journal Information:
Journal Volume: 28; Journal Issue: 13; Journal ID: ISSN 0277-5387
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; CHEMISTRY; CRYSTAL STRUCTURE; MASS SPECTROSCOPY; X-RAY DIFFRACTION

Citation Formats

Poola, Bhaskar, and Richmond, Michael G. 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). United States: N. p., 2009. Web. doi:10.1016/j.poly.2009.05.049.
Poola, Bhaskar, & Richmond, Michael G. 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). United States. doi:10.1016/j.poly.2009.05.049.
Poola, Bhaskar, and Richmond, Michael G. Thu . "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)". United States. doi:10.1016/j.poly.2009.05.049.
@article{osti_1045247,
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)},
author = {Poola, Bhaskar and Richmond, Michael G},
abstractNote = {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.},
doi = {10.1016/j.poly.2009.05.049},
journal = {Polyhedron},
issn = {0277-5387},
number = 13,
volume = 28,
place = {United States},
year = {2009},
month = {1}
}