Synthesis of dimethylmanganese(II) complexes bearing N-heterocyclic carbenes and nucleophilic substitution reaction of tetraalkoxysilanes by diorganomanganese(II) complexes
作者:Takayoshi Hashimoto、Yuko Kawato、Yumiko Nakajima、Yasuhiro Ohki、Kazuyuki Tatsumi、Wataru Ando、Kazuhiko Sato、Shigeru Shimada
DOI:10.1016/j.jorganchem.2016.07.025
日期:2016.10
Reactions of manganese(II) dichlorides bearing a N-heterocyclic carbene ligand (L), [MnCl(μ-Cl)(L)]2 (1a, L = 1,3-diisopropyl-4,5-dimethylimidazole-2-ylidene (IiPr); 1b, L = 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene (IMes); 1c, L = 1,3-bis(2,6-diisopropylphenyl)imidazole-2-ylidene (IPr)) with MeLi afford the dinuclear dimethylmanganese(II) complexes, [MnMe(μ-Me)(L)]2 (2a, L = IiPr; 2b, L = IMes;
带有N杂环卡宾配体(L),[MnCl(μ- Cl)(L)] 2(1a,L = 1,3-二异丙基-4,5-二甲基咪唑-2-亚基的二氯化锰(II)的反应(I我PR);图1b,L = 1,3-双(2,4,6-三甲基苯基)咪唑-2-亚基(IMES); 1C,L = 1,3-双(2,6-二异丙基)咪唑-2-亚基(IPR)),与将MeLi得到双核dimethylmanganese(II)配合物,[MnMe(μ -Me)(L)] 2(2A,L = I我镨;图2b,L = IMES;图2c,L = IPr)。配合物2a - c实现Si(OEt)4的亲核取代,以选择性地形成MeSi(OEt)3。相关的芳基锰(II)络合物类似地与Si(OEt)4反应,得到ArSi(OEt)3和Ar 2 Si(OEt)2(Ar = Ph,2,6-Me 2(C 6 H 3))。动力学研究支持观察到的Si(OEt)4转化的缔合机制