Synthesis, structure, and fluxional behavior of 1,2,3,4-tetramethylfulvene- bridged diruthenium complexes

Hisako Hashimoto, Hiromi Tobita, Hiroshi Ogino

Research output: Contribution to journalArticlepeer-review

14 Citations (Scopus)

Abstract

A new diruthenium complex (η15-CH 2C5Me4)Ru2(CO)6 (1) was synthesized by the reaction of 1,2,3,4-tetramethylfulvene and Ru 3(CO)12 in 49% yield. The X-ray crystal structure of 1 revealed that the fulvene ligand bridges over two ruthenium atoms in an η15-fashion. Fluxionality of the carbonyl ligands of 1 was studied in detail by line-shape analysis for the signals of the carbonyl ligands in the variable-temperature 13C NMR spectra (150 MHz), which revealed the existence of two processes. Mechanisms of the two processes were suggested based on the activation parameters, ΔH , ΔS, and ΔG 298: process I (fast process) is an intramolecular and global exchange of five carbonyl ligands between two Ru atoms probably by way of a carbonyl-bridged structure, and process II (slow process) corresponds to the participation of the last carbonyl ligand to the exchange. Interestingly, the carbonyl exchange was completely suppressed in the case of (η15-CH2C5Me 4)Ru2(CO)5(PMe3) (2) which was obtained by the reaction of 1 with PMe3.

Original languageEnglish
Pages (from-to)347-354
Number of pages8
JournalInorganica Chimica Acta
Volume350
DOIs
Publication statusPublished - 2003 Jul 4

Keywords

  • Carbonyl exchange
  • Crystal structures
  • Diruthenium complexes
  • Fluxional behavior
  • Fulvene
  • Tetramethylfulvene

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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