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Title: Synthesis, Reactivity Investigation, and X-ray Diffraction Structures of New Platinum(II) Compounds Containing Redox-Active Diphosphine Ligands

Abstract

Substitution of the 1,5-cyclooctadiene (cod) ligand in PtCl2(cod) (1) by the diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) yields PtCl2(bpcd) (2). Knoevenagel condensation of 2 with 9-anthracenecarboxaldehyde leads to the functionalization of the bpcd ligand and formation of the corresponding 2-(9-anthracenylidene)-4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (abpcd) substituted compound PtCl2(abpcd) (3), which is also obtained from the direct reaction of 1 with the abpcd ligand in near quantitative yield. The reaction of 3 with disodium maleonitriledithiolate (Na2mnt) affords the chelating dithiolate compound Pt(mnt)(abpcd) (4). Compounds 2 C4 have been fully characterized in solution by IR and NMR spectroscopies (1H and 31P), and their molecular structures established by X-ray crystallography. The electrochemical properties of 2 C4 have examined by cyclic voltammetry, and the nature of the HOMO and LUMO levels in these systems has been established by MO calculations at the extended H ckel level, the results of which are discussed with respect to electrochemical data and related diphosphine derivatives.

Authors:
 [1];  [2];  [2]
  1. ORNL
  2. University of North Texas
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
946493
DOE Contract Number:  
DE-AC05-00OR22725
Resource Type:
Journal Article
Journal Name:
Journal of Molecular Structure
Additional Journal Information:
Journal Volume: 919; Journal Issue: 1-3; Journal ID: ISSN 0022-2860
Country of Publication:
United States
Language:
English
Subject:
73 NUCLEAR PHYSICS AND RADIATION PHYSICS; CRYSTALLOGRAPHY; DIRECT REACTIONS; MOLECULAR STRUCTURE; SYNTHESIS; X-RAY DIFFRACTION

Citation Formats

Wang, Xiaoping, Richmond, Michael G., and Hunt, Sean W. Synthesis, Reactivity Investigation, and X-ray Diffraction Structures of New Platinum(II) Compounds Containing Redox-Active Diphosphine Ligands. United States: N. p., 2009. Web.
Wang, Xiaoping, Richmond, Michael G., & Hunt, Sean W. Synthesis, Reactivity Investigation, and X-ray Diffraction Structures of New Platinum(II) Compounds Containing Redox-Active Diphosphine Ligands. United States.
Wang, Xiaoping, Richmond, Michael G., and Hunt, Sean W. Thu . "Synthesis, Reactivity Investigation, and X-ray Diffraction Structures of New Platinum(II) Compounds Containing Redox-Active Diphosphine Ligands". United States.
@article{osti_946493,
title = {Synthesis, Reactivity Investigation, and X-ray Diffraction Structures of New Platinum(II) Compounds Containing Redox-Active Diphosphine Ligands},
author = {Wang, Xiaoping and Richmond, Michael G. and Hunt, Sean W},
abstractNote = {Substitution of the 1,5-cyclooctadiene (cod) ligand in PtCl2(cod) (1) by the diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) yields PtCl2(bpcd) (2). Knoevenagel condensation of 2 with 9-anthracenecarboxaldehyde leads to the functionalization of the bpcd ligand and formation of the corresponding 2-(9-anthracenylidene)-4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (abpcd) substituted compound PtCl2(abpcd) (3), which is also obtained from the direct reaction of 1 with the abpcd ligand in near quantitative yield. The reaction of 3 with disodium maleonitriledithiolate (Na2mnt) affords the chelating dithiolate compound Pt(mnt)(abpcd) (4). Compounds 2 C4 have been fully characterized in solution by IR and NMR spectroscopies (1H and 31P), and their molecular structures established by X-ray crystallography. The electrochemical properties of 2 C4 have examined by cyclic voltammetry, and the nature of the HOMO and LUMO levels in these systems has been established by MO calculations at the extended H ckel level, the results of which are discussed with respect to electrochemical data and related diphosphine derivatives.},
doi = {},
journal = {Journal of Molecular Structure},
issn = {0022-2860},
number = 1-3,
volume = 919,
place = {United States},
year = {2009},
month = {1}
}