The alkyne-bridged complex [Ir2Cl2(CO)(μ-DMA)(DPM)2] [DMA = di-Me acetylenedicarboxylate, DPM = bis(diphenylphosphino)methane] reacts with 1 equiv of CO, PMe3, P(OMe)3, or NCMe to give one of two types of species. Reaction with CO yields the complex [Ir2Cl2(CO)2(μ-DMA)(DPM)2], in which both carbonyl groups are terminally bound, one to each metal. However, reaction with L = PMe3, P(OMe)3, or NCMe yields the adduct [Ir2Cl2L(μ-CO)(μ-DMA)(DPM)2], in which the carbonyl group bridges the metals with no accompanying Ir-Ir bond. The long metal-metal sepn. of 3.4580 (7) Å results in a geometry at the bridging carbonyl ligand that is reminiscent of sp2 hybridization [Ir-C(O)-Ir angle of 119.4 (6)°].

Transformation of a terminal to a bridging carbonyl ligand accompanied by iridium-iridium bond cleavage: an example of transmission of electronic effects from one metal center to another

VASAPOLLO, Giuseppe;
1986-01-01

Abstract

The alkyne-bridged complex [Ir2Cl2(CO)(μ-DMA)(DPM)2] [DMA = di-Me acetylenedicarboxylate, DPM = bis(diphenylphosphino)methane] reacts with 1 equiv of CO, PMe3, P(OMe)3, or NCMe to give one of two types of species. Reaction with CO yields the complex [Ir2Cl2(CO)2(μ-DMA)(DPM)2], in which both carbonyl groups are terminally bound, one to each metal. However, reaction with L = PMe3, P(OMe)3, or NCMe yields the adduct [Ir2Cl2L(μ-CO)(μ-DMA)(DPM)2], in which the carbonyl group bridges the metals with no accompanying Ir-Ir bond. The long metal-metal sepn. of 3.4580 (7) Å results in a geometry at the bridging carbonyl ligand that is reminiscent of sp2 hybridization [Ir-C(O)-Ir angle of 119.4 (6)°].
File in questo prodotto:
Non ci sono file associati a questo prodotto.

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11587/366081
 Attenzione

Attenzione! I dati visualizzati non sono stati sottoposti a validazione da parte dell'ateneo

Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus ND
  • ???jsp.display-item.citation.isi??? ND
social impact