Crossover expts. using X2Os3(CO)10 and XCCCMe3(X = H or D) were conducted and the effects of deuterium substitution on the product distribution noted. A kinetic isotope effect is obsd. on the rate of formation of (.mu.-H)Os3(CO)10(trans-.sigma.-.pi.-.eta.2-.mu.-CH:CHR) (I) relative to the other two products of the reaction (.mu.-H)Os3(CO)10(.sigma.-.pi.-.eta.2-.mu.-C:CR) (II) and (.mu.-CO)Os3(CO)9(.eta.2-.mu.3-HCCR) (III). The crossover expts. demonstrate that II and III are not formed from I. A mechanism is presented which explains these results as well as the obsd. scrambling of H and D in the formation of I in terms of an extension of the known ligand dynamics of H2Os3(CO)10L complexes.

A mechanistic study of the reaction of H2Os3(CO)10 with terminal alkynes

MILONE, Luciano;AIME, Silvio;GOBETTO, Roberto;
1988

Abstract

Crossover expts. using X2Os3(CO)10 and XCCCMe3(X = H or D) were conducted and the effects of deuterium substitution on the product distribution noted. A kinetic isotope effect is obsd. on the rate of formation of (.mu.-H)Os3(CO)10(trans-.sigma.-.pi.-.eta.2-.mu.-CH:CHR) (I) relative to the other two products of the reaction (.mu.-H)Os3(CO)10(.sigma.-.pi.-.eta.2-.mu.-C:CR) (II) and (.mu.-CO)Os3(CO)9(.eta.2-.mu.3-HCCR) (III). The crossover expts. demonstrate that II and III are not formed from I. A mechanism is presented which explains these results as well as the obsd. scrambling of H and D in the formation of I in terms of an extension of the known ligand dynamics of H2Os3(CO)10L complexes.
GAZZETTA CHIMICA ITALIANA
118
299
304
hydride; triosmium; cluster; addition; terminal alkyne; deuterium exchange; acetylide; crossover experiment; reaction mechanism
Rosenberg Edward; Anslyn Eric V.; Milone Luciano; Aime Silvio; Gobetto Roberto; Osella Domenico
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2318/49900
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