铬(0)和钼(0)双（η(6)-芳烃）衍生物的合成及其单电子氧化为[M(η(6)-芳烃)(2)]⁺阳离子。

Synthesis of chromium(0) and molybdenum(0) bis (eta(6)-arene) derivatives and their monoelectronic oxidation to [M(eta(6)-arene)(2)](+) cations.

作者信息

Calucci Lucia, Cloke F Geoffrey N, Englert Ulli, Hitchcock Peter B, Pampaloni Guido, Pinzino Calogero, Puccini Filippo, Volpe Manuel

机构信息

Istituto per i Processi Chimico-Fisici, CNR, Area della Ricerca, Via G. Moruzzi 1, I-56124 Pisa, Italy.

出版信息

Dalton Trans. 2006 Sep 21(35):4228-34. doi: 10.1039/b602783k. Epub 2006 Jun 22.

DOI:10.1039/b602783k

PMID:16932815

Abstract

M(eta(6)-arene)(2) species (M = Cr, arene = 1,3,5-Me(3)C(6)H(3); M = Mo, arene = 1,3,5-Me(3)C(6)H(3), 1,3,5-(i)Pr(3)C(6)H(3)), have been prepared by a modified Fischer-Hafner synthesis or by metal vapour techniques. The reaction of Cr(eta(6)-1,3,5-Me(3)C(6)H(3))(2) with the fulvene derivatives pentacarbomethoxycyclopentadiene (pcmcpH), 1-benzoyl-6-hydroxy-6-phenylfulvene (dbcpH), or 1-benzoyl-3-nitro-6-hydroxy-6-phenylfulvene (dbncpH) proceeds with evolution of dihydrogen and formation of the ionic derivatives [Cr(eta(6)-1,3,5-Me(3)C(6)H(3))(2)][E], where E = pcmcp, dbcp, or dbncp. Mo(eta(6)-arene)(2) derivatives (arene = toluene, 1,3,5-Me(3)C(6)H(3), 1,3,5-(i)Pr(3)C(6)H(3)) are oxidized to Mo(eta(6)-arene)(2) by pcmcpH. The crystal and molecular structures of [M(eta(6)-1,3,5-R(3)C(6)H(3))(2)][pcmcp] (M = Cr, R = Me; M = Mo, R = Me, (i)Pr) have been solved by X-ray single crystal diffraction.

摘要

通过改进的费舍尔-哈夫纳合成法或金属气相技术制备了M(η(6)-芳烃)(2)物种（M = Cr，芳烃 = 1,3,5-三甲基苯；M = Mo，芳烃 = 1,3,5-三甲基苯，1,3,5-三异丙基苯）。Cr(η(6)-1,3,5-三甲基苯)(2)与富烯衍生物五碳甲氧基环戊二烯（pcmcpH）、1-苯甲酰基-6-羟基-6-苯基富烯（dbcpH）或1-苯甲酰基-3-硝基-6-羟基-6-苯基富烯（dbncpH）反应，会释放出氢气并形成离子衍生物[Cr(η(6)-1,3,5-三甲基苯)(2)][E]，其中E = pcmcp、dbcp或dbncp。Mo(η(6)-芳烃)(2)衍生物（芳烃 = 甲苯、1,3,5-三甲基苯、1,3,5-三异丙基苯）被pcmcpH氧化为[Mo(η(6)-芳烃)(2)]⁺。通过X射线单晶衍射解析了[M(η(6)-1,3,5-R(3)C(6)H(3))(2)][pcmcp]（M = Cr，R = Me；M = Mo，R = Me，(i)Pr）的晶体和分子结构。