Science and Mathematics Faculty Publications
Aufbau Approach to Multimetallic Ensembles Based on Tetrathiooxalate: [Cp*4Rh4(C2S4)2]2+, [Cp*3Rh2Ru(C2S4)]+, and [Cp*6Rh6(C2S4)2]4+
Document Type
Article
Publication Date
12-11-2000
Journal Title
Organometallics
Volume
19
Issue
25
First Page
5370
Last Page
5375
Abstract
Experiments aimed at the characterization of new coordination modes for tetrathiooxalate (TTO) are described. Cyclic voltammetric (CV) measurements on Cp*2Rh2(C2S4) (1) revealed an irreversible oxidation as part of an ECE process that results in the chemically reversible dimerization of 1+. Treatment of 1 with CpFe[C5H4C(O)Me]BF4 followed by anion exchange gave [Cp*4Rh4(C2S4)2](BPh4)2, the dication of which consists of a dimer of 1+ linked through two pairs of Rh−S bonds. A second new bonding mode for TTO was generated by treatment of 1 with [Cp*Ru(MeCN)3]PF6 to give [Cp*3Rh2Ru(C2S4)]+ (3) wherein Cp*Ru+ is η5-bonded to one RhS2C2 ring. A third new bonding mode for TTO is illustrated by [Cp*6Rh6(C2S4)2]4+, formed by the reaction of Cp*Rh(MeCN)32+ and 1. The structure can be viewed as a dimer of3, except that there are no M−M bonds: the Cp*Rh2+ fragments are bonded via an η4-interaction to RhS2C2 rings. Furthermore, the [Cp*3Rh3(C2S4)]2+ subunits, which are otherwise isoelectronic with 3, dimerize, such that all eight sulfur atoms are triply bridging.
Recommended Citation
Holloway, G. A.; Klausmeyer, K. K.; Wilson, S. R.; Rauchfuss, T. B. "Aufbau Approach to Multimetallic Ensembles Based on Tetrathiooxalate: [Cp*4Rh4(C2S4)2]2+, [Cp*3Rh2Ru(C2S4)]+, and [Cp*6Rh6(C2S4)2]4+," Organometallics 2000, 19, 5370-5375.
