Syntheses, Structures, and Reactivities of Heterobimetallic Bridging Dinitrogen Complexes Containing Group 6 and Group 4 or 5 Transition Metals
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- 作者：Hiroshige Ishino ; Tatsuya Nagano ; Shigeki Kuwata ; Youhei Yokobayashi ; Youichi Ishii ; Masanobu Hidai ; and Yasushi Mizobe
- 刊名：Organometallics
- 出版年：2001
- 出版时间：January 8, 2001
- 年：2001
- 卷：20
- 期：1
- 页码：188 - 198
- 全文大小：179K
- 年卷期：v.20,no.1(January 8, 2001)
- ISSN：1520-6041
文摘
A series of heterobimetallic dinitrogen complexes containing group 6 and group 4 or 5transition metals were synthesized by the reaction of the tungsten or molybdenum dinitrogencomplexes cis-[W(N2)2(PMe2Ph)4] (1) and trans-[M(N2)2(dppe)2] (2) (M = W, Mo) with group4 or group 5 compounds such as [CpTiCl3], [Cp2M'Cl2] (M' = Ti, Zr, Hf), or [Cp'M'Cl4] (Cp'= Cp, Cp*; M' = Nb, Ta). Crystallographic studies of the complexes thus obtained including[WCl(PMe2Ph)4(
-N2)TiCpCl2] and [WCl(PMe2Ph)4(-N2)NbCpCl3] revealed that the M-N-N-M' core is essentially linear, and the N-N bond is regarded to have the formal bondorder of 2. Several -N2 complexes with methyl ligands at the group 4 or 5 metal centerwere also obtained through the reaction of dinitrogen complexes 1 and 2a (M = W) with themethyl complexes [Cp2ZrMeCl], [TaMe3Cl2], and [NbMe2Cl3]. The reaction of the complex[WCl(dppe)2(-N2)TiCpCl2] with Li2S5 afforded the 
2-pentasulfido complex [WCl(dppe)2(-N2)TiCpS5], where the 2-S5 ligand forms a six-membered chelate ring with the chairconformation. Protonation of the -N2 complexes having PMe2Ph ligands gave NH3 inmoderate yield, concurrent with the formation of a small amount of NH2NH2.
-N2)TiCpCl2] and [WCl(PMe2Ph)4(-N2)NbCpCl3] revealed that the M-N-N-M' core is essentially linear, and the N-N bond is regarded to have the formal bondorder of 2. Several -N2 complexes with methyl ligands at the group 4 or 5 metal centerwere also obtained through the reaction of dinitrogen complexes 1 and 2a (M = W) with themethyl complexes [Cp2ZrMeCl], [TaMe3Cl2], and [NbMe2Cl3]. The reaction of the complex[WCl(dppe)2(-N2)TiCpCl2] with Li2S5 afforded the 2-pentasulfido complex [WCl(dppe)2(-N2)TiCpS5], where the 2-S5 ligand forms a six-membered chelate ring with the chairconformation. Protonation of the -N2 complexes having PMe2Ph ligands gave NH3 inmoderate yield, concurrent with the formation of a small amount of NH2NH2.