Carbonyl Substitution and Ring Slippage upon Reaction of Trialkylphosphines with (Fulvalene)diruthenium Tetracarbonyl. X-ray Structural Analysis of (η°:η4-C10H8)Ru(PMe3)2CO and Fluxional Behavior of (η5: η5-C10H8)RU 2(CO)3L. (L = Phosphine)

Roland Boese, William B. Tolman, K. Peter Vollhardt

Research output: Contribution to journalArticlepeer-review

18 Scopus citations

Abstract

Treatment of (η55-fulvalene)diruthenium tetracarbonyl [FvRu2(CO)4, 3] with a large excess (8–10 equiv) of PMe3 at 120 °C provides trans -Ru(CO)3(PMe3)2 (7) and FvRu(PMe3)2(CO) (6), in which only one Cp ring is bonded to Ru. Complex 6 was characterized by X-ray crystallography: orthorhombic, a = 1464.3 (4) pm, b = 1535.1 (2) pm, c = 1691.6 (4) pm, space group Pbca. Reaction of 3 with 2–3 equiv of PMe3 or excess (5 equiv) PEt3 gives FvRu2(CO)3L (4, 5). Both substitution products are fluxional on the NMR time scale and a mechanism involving reversible terminal to bridged carbonyl exchange is proposed. Activation parameters for the process were determined from a line-shape analysis of variable-temperature 13C NMR spectra of 13CO-labeled 5.

Original languageEnglish (US)
Pages (from-to)582-584
Number of pages3
JournalOrganometallics
Volume5
Issue number3
DOIs
StatePublished - Jan 1 1986

Fingerprint Dive into the research topics of 'Carbonyl Substitution and Ring Slippage upon Reaction of Trialkylphosphines with (Fulvalene)diruthenium Tetracarbonyl. X-ray Structural Analysis of (η°:η<sup>4</sup>-C<sub>10</sub>H<sub>8</sub>)Ru(PMe<sub>3</sub>)<sub>2</sub>CO and Fluxional Behavior of (η<sup>5</sup>: η5-C10H8)RU <sub>2</sub>(CO)<sub>3</sub>L. (L = Phosphine)'. Together they form a unique fingerprint.

Cite this