Do early and late transition metal noble gas complexes react by different mechanisms? A room temperature time-resolved infrared study of (η5-C5R5)Rh(CO)2 (R = H or Me) in supercritical noble gas solution at room temperature

Omar S. Jina, Xue Z. Sun, Michael W. George

Research output: Journal PublicationArticlepeer-review

12 Citations (Scopus)

Abstract

Using fast time-resolved infrared spectroscopy, the late transition metal noble gas complexes CpRh(CO)(L) and Cp*Rh(CO)(L) (Cp = η5-C5H5; Cp* = η5- C5Me5; L = Xe and Kr) have been characterized at room temperature in supercritical noble gas solution. The krypton complexes are more reactive than the corresponding xenon compounds. There is a significant difference in reactivity with CO between CpRh(CO)(L) and Cp*Rh(CO)(L) with CpRh(CO)(Xe) (kco = 6.7 × 105 dm3 mol-1 s-1) being ca. 20 times less reactive than Cp*Rh(CO)(Xe) (kco = 1.4 × 107 dm3 mol-1 s-1). Similarly CpRh(CO)(Kr) (kco = 1.3 × 108 dm3 mol-1 s-1) is also less reactive than Cp*Rh(CO)(Kr) (kco = 4.3 × 10 8 dm3 mol-1 s-1). This should be contrasted to the early transition metal noble gas complexes, where for a given metal-noble gas complex, CpM(CO)2(L) and Cp*M(CO) 2(L) (M = Mn or Re) have similar reactivity towards CO. The activation parameters for the reaction of CpRh(CO)(L) and Cp*Rh(CO)(L) with CO have been determined above room temperature, and suggest that the reaction proceeds by an associative mechanism.

Original languageEnglish
Pages (from-to)1773-1778
Number of pages6
JournalDalton Transactions
Issue number9
DOIs
Publication statusPublished - 7 May 2003

ASJC Scopus subject areas

  • Inorganic Chemistry

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