Comparative Reactivity of Triruthenium and Triosmium 3-
详细信息 查看全文
- 作者：Edward Rosenberg ; Luciano Milone ; Roberto Gobetto ; Domenico Osella ; Kenneth Hardcastle ; Sharad Hajela ; Kate Moizeau ; Michael Day ; Erich Wolf ; and David Espitia
- 刊名：Organometallics
- 出版年：1997
- 出版时间：June 10, 1997
- 年：1997
- 卷：16
- 期：12
- 页码：2665 - 2673
- 全文大小：372K
- 年卷期：v.16,no.12(June 10, 1997)
- ISSN：1520-6041
文摘
The reactivity and ligand dynamics of the
3-
2-imidoyl clustersRu3(CO)9(3-2-RC=NR')(-H) (R = CH3, R' = Et 2; RR' =(CH2)3, 3; RR' =(CH2)2C(H)CH2OCH34, R = R' = CH3, 5)are compared with the previously reported osmium analogs. Thelowest energy dynamicalprocess in these clusters is the "windshield wiper" motion over theface of the cluster whereastripodal rotation of the carbonyl groups on the unbridged metal atom isthe fastest processin the analogous osmium compounds. Although the structures of thephosphine andisocyanide substitution products reported,Ru3(CO)8(3-2-RC=NR')(-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), areidentical to their osmium analogs, the pathway to theirformation reflects the lower CO dissociation energies for rutheniumclusters and a greatersensitivity to the substituents on the imidoyl group. The solidstate structures of 9 and 12are reported as well as that ofOs3(CO)8(-2-C=N(CH2)3(-H)(PPh3)(MeNC)(15). The latterillustrates the hemilabile nature of the 3-imidoylligand even in phosphine-substitutedderivatives and the structural preferences of phosphine and isocyanideligands in this classof clusters.
3-2-imidoyl clustersRu3(CO)9(3-2-RC=NR')(-H) (R = CH3, R' = Et 2; RR' =(CH2)3, 3; RR' =(CH2)2C(H)CH2OCH34, R = R' = CH3, 5)are compared with the previously reported osmium analogs. Thelowest energy dynamicalprocess in these clusters is the "windshield wiper" motion over theface of the cluster whereastripodal rotation of the carbonyl groups on the unbridged metal atom isthe fastest processin the analogous osmium compounds. Although the structures of thephosphine andisocyanide substitution products reported,Ru3(CO)8(3-2-RC=NR')(-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), areidentical to their osmium analogs, the pathway to theirformation reflects the lower CO dissociation energies for rutheniumclusters and a greatersensitivity to the substituents on the imidoyl group. The solidstate structures of 9 and 12are reported as well as that ofOs3(CO)8(-2-C=N(CH2)3(-H)(PPh3)(MeNC)(15). The latterillustrates the hemilabile nature of the 3-imidoylligand even in phosphine-substitutedderivatives and the structural preferences of phosphine and isocyanideligands in this classof clusters.