Carbon-nitrogen bond rotation in a dithiocarbamato complex of rhodium(iii)

Bruce M. Mattson; A. E. Madera

doi:10.1080/00958978408073885

Carbon-nitrogen bond rotation in a dithiocarbamato complex of rhodium(iii)

Bruce M. Mattson, A. E. Madera

Department of Chemistry

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5 Scopus citations

Abstract

The temperature-dependent pmr spectrum of Rh(MePhdtc)3 was examined in CDC13 solvent over the temperature range —34° to +51°. The complex is stereochemically non-rigid and isomerizes by a C-N bond rotation mechanism. A line shape analysis yielded a value of ΔG‡= 61.5 ± 4.2 kJ mol-1. This barrier to rotation is large relative to similar complexes of Fe(II) and Fe(III) but similar to values for Fe(IV) and Co(III). Metal-centered optical inversion is slow over the temperature range studied.

Original language	English
Pages (from-to)	321-324
Number of pages	4
Journal	Journal of Coordination Chemistry
Volume	13
Issue number	4
DOIs	https://doi.org/10.1080/00958978408073885
Publication status	Published - 1984

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All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Materials Chemistry

Cite this

Mattson, B. M., & Madera, A. E. (1984). Carbon-nitrogen bond rotation in a dithiocarbamato complex of rhodium(iii). Journal of Coordination Chemistry, 13(4), 321-324. https://doi.org/10.1080/00958978408073885

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AB - The temperature-dependent pmr spectrum of Rh(MePhdtc)3 was examined in CDC13 solvent over the temperature range —34° to +51°. The complex is stereochemically non-rigid and isomerizes by a C-N bond rotation mechanism. A line shape analysis yielded a value of ΔG‡= 61.5 ± 4.2 kJ mol-1. This barrier to rotation is large relative to similar complexes of Fe(II) and Fe(III) but similar to values for Fe(IV) and Co(III). Metal-centered optical inversion is slow over the temperature range studied.

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10.1080/00958978408073885