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Synthesis and reactivities of the 17 e- complex [ReIIBr4(CO)2]2-: A convenient entry into Rhenium(II) chemistry


Zobi, F; Kromer, L; Spingler, B; Alberto, R (2009). Synthesis and reactivities of the 17 e- complex [ReIIBr4(CO)2]2-: A convenient entry into Rhenium(II) chemistry. Inorganic Chemistry, 48(18):8965-8970.

Abstract

The reduction of (Et4N)[ReIIIBr4(CO)2] (1) by 0.5 equiv of tetrakis-dimethylaminoethylene in acetonitrile yields directly the air-stable, 17-electron ReII synthon (Et4N)2[ReIIBr4(CO)2] (2) in nearly quantitative yield. The versatility of 2 as a synthon for ReII chemistry was demonstrated by substitution reactions of [ReIIBr4(CO)2]2− with different mono-, bi-, and tridentate ligands. The resulting ReII complexes form highly crystalline compounds, and the solid state structures of the neutral trans−cis-[ReIIBr2(CO)2(X)n] species (where X = imidazole, pyridine, or phenanthroline) could be determined. All complexes are stable under aerobic conditions, both as solids and in solution, and showed fully reversible one-electron ReII → ReI reductions between ca. −70 and −120 mV. Carbonyl stretching frequencies (νCO) of this new family of ReII complexes are observed in the 1990 cm−1 (A1) and 1830 (Eg) cm−1 regions. With complex 2, a wide variety of fundamental but so far unknown ReII complexes become accessible via facile substitution reactions.

Abstract

The reduction of (Et4N)[ReIIIBr4(CO)2] (1) by 0.5 equiv of tetrakis-dimethylaminoethylene in acetonitrile yields directly the air-stable, 17-electron ReII synthon (Et4N)2[ReIIBr4(CO)2] (2) in nearly quantitative yield. The versatility of 2 as a synthon for ReII chemistry was demonstrated by substitution reactions of [ReIIBr4(CO)2]2− with different mono-, bi-, and tridentate ligands. The resulting ReII complexes form highly crystalline compounds, and the solid state structures of the neutral trans−cis-[ReIIBr2(CO)2(X)n] species (where X = imidazole, pyridine, or phenanthroline) could be determined. All complexes are stable under aerobic conditions, both as solids and in solution, and showed fully reversible one-electron ReII → ReI reductions between ca. −70 and −120 mV. Carbonyl stretching frequencies (νCO) of this new family of ReII complexes are observed in the 1990 cm−1 (A1) and 1830 (Eg) cm−1 regions. With complex 2, a wide variety of fundamental but so far unknown ReII complexes become accessible via facile substitution reactions.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:2009
Deposited On:23 Jan 2010 19:34
Last Modified:06 Dec 2017 23:30
Publisher:American Chemical Society
ISSN:0020-1669
Publisher DOI:https://doi.org/10.1021/ic901031x

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