Synthesis of a Sulfido-Capped Trinuclear Cluster [{(5-C5Me5)Ir}2{Mo(CO)3}(
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- 作者：Hidenobu Kajitani ; Hidetake Seino ; Yasushi Mizobe
- 刊名：Organometallics
- 出版年：2007
- 出版时间：July 2, 2007
- 年：2007
- 卷：26
- 期：14
- 页码：3499 - 3508
- 全文大小：267K
- 年卷期：v.26,no.14(July 2, 2007)
- ISSN：1520-6041
文摘
Treatment of a hydrosulfido-bridged diiridium complex, [(Cp*IrCl)2(
-SH)2] (1; Cp* = 
5-C5Me5),with [Mo(6-toluene)(CO)3] in the presence of NEt3 gave the sulfido-bridged Ir2Mo cluster [(Cp*Ir)2{Mo(CO)3}(3-S)2] (3). Detailed studies on the reactivity of its Mo site have resulted in the isolation ofa series of new Ir2Mo(3-S)2 clusters. Thus, 3 reacted with Ph2PCH2CH2PPh2 (dppe) to afford [(Cp*Ir)2{Mo(CO)(dppe)}(3-S)2] (4), which underwent the oxidation by I2 at the molybdenum site to give [(Cp*Ir)2{MoI(CO)(dppe)}(3-S)2]I (5). On the other hand, oxidation of 3 with [Cp2Fe][PF6] in THF-MeCNresulted in the elimination of one CO ligand and concomitant coordination of two MeCN molecules atthe Mo center, yielding [(Cp*Ir)2{Mo(CO)2(MeCN)2}(3-S)2][PF6]2 (6). Further oxidation of 6 using O2gas led to the elimination of all the remaining CO ligands to give an oxo-dichloro cluster, [(Cp*Ir)2(MoOCl2)(3-S)2] (7). The ligation of diphosphines to the molybdenum site in 7 formed the cationicoxo-chloro cluster [(Cp*Ir)2{MoOCl(R2PC2H4PR2)}(3-S)2]X (8a, R = Me (dmpe), X = Cl; 8b, R = Et,X = Cl; 8c, R = Ph, X = PF6) with concurrent dissociation of one of the Cl ligands, and the followingdeoxygenation from 8a with BCl3 gave [(Cp*Ir)2{MoCl3(dmpe)}(3-S)2][BCl4] (9). Reduction of 9 withCp2Co afforded a paramagnetic Mo(III) cluster, [(Cp*Ir)2{MoCl2(dmpe)}(3-S)2][BCl4] (11), whereasreduction of 8c with NaBH4 resulted in the formation of a Mo(II) dihydrido cluster, [(Cp*Ir)2{MoH2(dppe)}(3-S)2] (12). X-ray analyses have been undertaken to determine the detailed structures for 3, 4,5, 6, 7, 8b, 9, and 12.
-SH)2] (1; Cp* = 5-C5Me5),with [Mo(6-toluene)(CO)3] in the presence of NEt3 gave the sulfido-bridged Ir2Mo cluster [(Cp*Ir)2{Mo(CO)3}(3-S)2] (3). Detailed studies on the reactivity of its Mo site have resulted in the isolation ofa series of new Ir2Mo(3-S)2 clusters. Thus, 3 reacted with Ph2PCH2CH2PPh2 (dppe) to afford [(Cp*Ir)2{Mo(CO)(dppe)}(3-S)2] (4), which underwent the oxidation by I2 at the molybdenum site to give [(Cp*Ir)2{MoI(CO)(dppe)}(3-S)2]I (5). On the other hand, oxidation of 3 with [Cp2Fe][PF6] in THF-MeCNresulted in the elimination of one CO ligand and concomitant coordination of two MeCN molecules atthe Mo center, yielding [(Cp*Ir)2{Mo(CO)2(MeCN)2}(3-S)2][PF6]2 (6). Further oxidation of 6 using O2gas led to the elimination of all the remaining CO ligands to give an oxo-dichloro cluster, [(Cp*Ir)2(MoOCl2)(3-S)2] (7). The ligation of diphosphines to the molybdenum site in 7 formed the cationicoxo-chloro cluster [(Cp*Ir)2{MoOCl(R2PC2H4PR2)}(3-S)2]X (8a, R = Me (dmpe), X = Cl; 8b, R = Et,X = Cl; 8c, R = Ph, X = PF6) with concurrent dissociation of one of the Cl ligands, and the followingdeoxygenation from 8a with BCl3 gave [(Cp*Ir)2{MoCl3(dmpe)}(3-S)2][BCl4] (9). Reduction of 9 withCp2Co afforded a paramagnetic Mo(III) cluster, [(Cp*Ir)2{MoCl2(dmpe)}(3-S)2][BCl4] (11), whereasreduction of 8c with NaBH4 resulted in the formation of a Mo(II) dihydrido cluster, [(Cp*Ir)2{MoH2(dppe)}(3-S)2] (12). X-ray analyses have been undertaken to determine the detailed structures for 3, 4,5, 6, 7, 8b, 9, and 12.© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |