C- and Z-shaped coordination compounds. Synthesis, structure, and spectroelectrochemistry of cis- and trans-[Re(CO)3(L)] 2-2,2′-bisbenzimidizolate with L = 4-phenylpyridine, 2,4′-bipyridine, or pyridine

Peter H. Dinolfo, Kurt D. Benkstein, Charlotte L. Stern, Joseph T Hupp

Research output: Contribution to journalArticle

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Abstract

A series of C- and Z-shaped complexes of the form cis- and trans-[Re(CO)3(L)]2BiBzIm, where L = 4-phenylpyridine, 2,4′-bipyridine, or pyridine and BiBzIm = 2,2′-bisbenzimidizolate, have been synthesized by the reaction of [Re(CO)4]2BiBzIm with a slight excess of L in refluxing tetrahydrofuran. Five of the six compounds have been isolated and crystallographically and electrochemically characterized. Formation of the sixth, the cis form of the [Re(CO) 3(4-phenylpyridine)]2BiBzIm, is evidently inhibited by the torsional steric demands of proximal 4-phenylpyridines. The compounds are acyclic analogues of recently studied tetrarhenium molecular rectangles and are of interest, in part, because of their potential to form ligand-centered mixed-valence (LCMV) compounds upon reduction by one electron. Spectroelectrochemical measurements corroborated the formation of a LCMV version of cis-[Re(CO)3(L)]2BiBzIm but failed to uncover a ligand-based intervalence transition. Electrochemical measurements revealed isomer-dependent L/L electrostatic effects, resulting in greater mixed-valence ion comproportionation for C-shaped assemblies versus Z-shaped assemblies.

Original languageEnglish
Pages (from-to)8707-8714
Number of pages8
JournalInorganic Chemistry
Volume44
Issue number24
DOIs
Publication statusPublished - Nov 28 2005

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Spectroelectrochemistry
Carbon Monoxide
pyridines
valence
assemblies
ligands
synthesis
Ligands
rectangles
tetrahydrofuran
isomers
Isomers
analogs
electrostatics
Electrostatics
Ions
4-phenylpyridine
pyridine
Electrons
ions

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

C- and Z-shaped coordination compounds. Synthesis, structure, and spectroelectrochemistry of cis- and trans-[Re(CO)3(L)] 2-2,2′-bisbenzimidizolate with L = 4-phenylpyridine, 2,4′-bipyridine, or pyridine. / Dinolfo, Peter H.; Benkstein, Kurt D.; Stern, Charlotte L.; Hupp, Joseph T.

In: Inorganic Chemistry, Vol. 44, No. 24, 28.11.2005, p. 8707-8714.

Research output: Contribution to journalArticle

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AB - A series of C- and Z-shaped complexes of the form cis- and trans-[Re(CO)3(L)]2BiBzIm, where L = 4-phenylpyridine, 2,4′-bipyridine, or pyridine and BiBzIm = 2,2′-bisbenzimidizolate, have been synthesized by the reaction of [Re(CO)4]2BiBzIm with a slight excess of L in refluxing tetrahydrofuran. Five of the six compounds have been isolated and crystallographically and electrochemically characterized. Formation of the sixth, the cis form of the [Re(CO) 3(4-phenylpyridine)]2BiBzIm, is evidently inhibited by the torsional steric demands of proximal 4-phenylpyridines. The compounds are acyclic analogues of recently studied tetrarhenium molecular rectangles and are of interest, in part, because of their potential to form ligand-centered mixed-valence (LCMV) compounds upon reduction by one electron. Spectroelectrochemical measurements corroborated the formation of a LCMV version of cis-[Re(CO)3(L)]2BiBzIm but failed to uncover a ligand-based intervalence transition. Electrochemical measurements revealed isomer-dependent L/L electrostatic effects, resulting in greater mixed-valence ion comproportionation for C-shaped assemblies versus Z-shaped assemblies.

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