Comparative reactivity of triruthenium and triosmium μ32-Imidoyls.1.Dynamics and reactions with carbon monoxide, phosphine, and isocyanide

Edward Rosenberg, Luciano Milone, Roberto Gobetto, Domenico Osella, Kenneth Hardcastle, Sharad Hajela, Kate Moizeau, Michael Day, Erich Wolf, David David

Risultato della ricerca: Contributo su rivistaArticolo in rivistapeer review

Abstract

The reactivity and ligand dynamics of the μ32-imidoyl clusters Ru3(CO)932-RC=NR′)-(μ-H) (R = CH3, R′ = Et 2; RR′ = (CH2)3, 3; RR′ = (CH2)2C(H)CH2OCH3 4, R = R′ = CH3, 5) are compared with the previously reported osmium analogs. The lowest energy dynamical process in these clusters is the "windshield wiper" motion over the face of the cluster whereas tripodal rotation of the carbonyl groups on the unbridged metal atom is the fastest process in the analogous osmium compounds. Although the structures of the phosphine and isocyanide substitution products reported, Ru3(CO)832-RC=NR′)(μ-H)L (R = CH3, R′ = CH2CH3, L = PPh3 (8a), L = CNMe (12); R = R′ = (CH2)3, L = PPh3 (9), L = CNMe (13); R = R′ = CH3, L = PPh3 (10), are identical to their osmium analogs, the pathway to their formation reflects the lower CO dissociation energies for ruthenium clusters and a greater sensitivity to the substituents on the imidoyl group. The solid state structures of 9 and 12 are reported as well as that of Os3(CO)8(μ-η2-C=N(CH2) 3(μ-H)(PPh3)(MeNC) (15). The latter illustrates the hemilabile nature of the μ3-imidoyl ligand even in phosphine-substituted derivatives and the structural preferences of phosphine and isocyanide ligands in this class of clusters.

Lingua originaleInglese
pagine (da-a)2665-2673
Numero di pagine9
RivistaOrganometallics
Volume16
Numero di pubblicazione12
DOI
Stato di pubblicazionePubblicato - 1 gen 1997
Pubblicato esternamente

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