Two-electron reduction of a Rh-Mo-Rh dithiolato complex to form a triplet ground state associated with a change in CO coordination mode.
J Am Chem Soc
; 131(4): 1388-9, 2009 Feb 04.
Article
em En
| MEDLINE
| ID: mdl-19138070
ABSTRACT
We synthesized a dithiolato-bridged heterometal trinuclear complex [{(eta(5)-C(5)Me(5))Rh(S(2)C(6)H(4))}(2)Mo(CO)(2)] (1) in which two rhodadithiolene complex units are bridged by a Mo(CO)(2) moiety. Complex 1 with a Rh(III)-Mo(0)-Rh(III) bond exhibits reversible one-step two-electron reduction with potential inversion. This redox process between 1 and 1(2-) accompanies a reversible structural change, which is an alternation in the CO coordination mode between semibridging and bridging. The ground state of dianion 1(2-) with a Rh(II)-Mo(0)-Rh(II) bond is assigned to spin triplet. These alternations of CO coordination mode and spin state are fully consistent with the density functional theory calculation results. This is the first example of multinuclear metalladithiolene complex which was successful in elucidating a reversible multielectron redox process associated with structural change and spin state change.
Texto completo:
1
Base de dados:
MEDLINE
Assunto principal:
Ródio
/
Compostos de Sulfidrila
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Monóxido de Carbono
/
Elétrons
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Molibdênio
Tipo de estudo:
Risk_factors_studies
Idioma:
En
Ano de publicação:
2009
Tipo de documento:
Article