Synthesis of Oxo- and Sulfido-Bridged Germanium-Ruthenium Complexes and Reactions on the Chalcogenido Bridges
详细信息 查看全文
- 作者：Tsuyoshi Matsumoto ; Yukiko Nakaya ; Kazuyuki Tatsumi
- 刊名：Organometallics
- 出版年：2006
- 出版时间：September 25, 2006
- 年：2006
- 卷：25
- 期：20
- 页码：4835 - 4845
- 全文大小：236K
- 年卷期：v.25,no.20(September 25, 2006)
- ISSN：1520-6041
文摘
A series of heterodinuclear germanium-ruthenium complexes having sulfido/oxo bridges, Dmp(Dep)Ge(
-E1)(-E2)Ru(
6-arene) (E1, E2 = S, O; arene = benzene, p-cymene; Dmp = 2,6-dimesitylphenyl,Dep = 2,6-diethylphenyl) were synthesized by the reaction of [Ru(6-arene)Cl2]2 and the correspondingdiarylgermanedichalcogenoles, Dmp(Dep)Ge(E1H)(E2H). The reaction with tertiary phosphines gave thecorresponding adducts Dmp(Dep)Ge(-S)(-E)Ru(PR3) (E = S, O; R = Ph, Et), in which the areneligand on the ruthenium was replaced by a mesityl group of Dmp. When Dmp(Dep)Ge(-S)2Ru(PPh3)was treated with the Br
nsted acids H(OEt2)2BArF4 and HOTf, a sulfido bridge was protonated to afford[Dmp(Dep)Ge(-S)(-SH)Ru(PPh3)]X (X = BArF4, OTf). Likewise, the methylation reaction withMe3OBF4 proceeded at a -S, generating [Dmp(Dep)Ge(-S)(-SMe)Ru(PPh3)](BF4). On the other hand,protonation of Dmp(Dep)Ge(-S)(-O)Ru(PPh3) gave a -OH complex, [Dmp(Dep)Ge(-S)(-OH)Ru(PPh3)]+, while the analogous methylation afforded the cationic -SMe complex [Dmp(Dep)Ge(-SMe)(-O)Ru(PPh3)]+.
-E1)(-E2)Ru(6-arene) (E1, E2 = S, O; arene = benzene, p-cymene; Dmp = 2,6-dimesitylphenyl,Dep = 2,6-diethylphenyl) were synthesized by the reaction of [Ru(6-arene)Cl2]2 and the correspondingdiarylgermanedichalcogenoles, Dmp(Dep)Ge(E1H)(E2H). The reaction with tertiary phosphines gave thecorresponding adducts Dmp(Dep)Ge(-S)(-E)Ru(PR3) (E = S, O; R = Ph, Et), in which the areneligand on the ruthenium was replaced by a mesityl group of Dmp. When Dmp(Dep)Ge(-S)2Ru(PPh3)was treated with the Brnsted acids H(OEt2)2BArF4 and HOTf, a sulfido bridge was protonated to afford[Dmp(Dep)Ge(-S)(-SH)Ru(PPh3)]X (X = BArF4, OTf). Likewise, the methylation reaction withMe3OBF4 proceeded at a -S, generating [Dmp(Dep)Ge(-S)(-SMe)Ru(PPh3)](BF4). On the other hand,protonation of Dmp(Dep)Ge(-S)(-O)Ru(PPh3) gave a -OH complex, [Dmp(Dep)Ge(-S)(-OH)Ru(PPh3)]+, while the analogous methylation afforded the cationic -SMe complex [Dmp(Dep)Ge(-SMe)(-O)Ru(PPh3)]+.