Catalysis of a high spin metal species

Research Project

Project/Area Number	26620052
Research Category	Grant-in-Aid for Challenging Exploratory Research
Allocation Type	Multi-year Fund
Research Field	Inorganic chemistry
Research Institution	National Institute of Advanced Industrial Science and Technology
Principal Investigator	Nakajima Yumiko 国立研究開発法人産業技術総合研究所, 触媒化学融合研究センター, 研究チーム長 (80462711)
Project Period (FY)	2014-04-01 – 2017-03-31
Project Status	Completed (Fiscal Year 2016)
Budget Amount *help	¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000) Fiscal Year 2015: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000) Fiscal Year 2014: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000)
Keywords	高スピン / マンガン / 求核剤 / アルコキシシラン / 3d金属 / 高スピン金属錯体
Outline of Final Research Achievements	This research project aims at the investigation of the catalysis of high-spin metal complexes, such as manganese (II) species. Reactions of manganese(II) dichloride bearing a N-heterocyclic carbene ligand (L), [MnCl(myu-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 afforded the dinuclear dimethylmanganese(II) complexes, [MnMe(myu-Me)(L)]2 (2a, L = IiPr; 2b, L = IMes; 2c, L = IPr). Complexes 2a-c achieved nucleophilic substitution of Si(OEt)4 to selectively form MeSi(OEt)3. Related arylmanganese(II) complexes analogously reacted with Si(OEt)4 to afford ArSi(OEt)3 and Ar2Si(OEt)2 (Ar = Ph, 2,6-Me2(C6H3)). Kinetic studies supported an associative mechanism for the observed transformation of Si(OEt)4, in which both the manganese species and Si(OEt)4 are involved in the rate-limiting step.