Issue 9, 2003

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

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 × 108 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.

Graphical abstract: 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

Article information

Article type
Paper
Submitted
16 Jul 2002
Accepted
02 Dec 2002
First published
07 Apr 2003

Dalton Trans., 2003, 1773-1778

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

O. S. Jina, X. Z. Sun and M. W. George, Dalton Trans., 2003, 1773 DOI: 10.1039/B206945H

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