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 language | English |
|---|---|
| Pages (from-to) | 8707-8714 |
| Number of pages | 8 |
| Journal | Inorganic Chemistry |
| Volume | 44 |
| Issue number | 24 |
| DOIs | |
| Publication status | Published - Nov 28 2005 |
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ASJC Scopus subject areas
- Inorganic Chemistry
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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 journal › Article
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TY - JOUR
T1 - 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
AU - Dinolfo, Peter H.
AU - Benkstein, Kurt D.
AU - Stern, Charlotte L.
AU - Hupp, Joseph T
PY - 2005/11/28
Y1 - 2005/11/28
N2 - 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.
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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U2 - 10.1021/ic050894u
DO - 10.1021/ic050894u
M3 - Article
VL - 44
SP - 8707
EP - 8714
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 24
ER -