A Two-Coordinate Manganese(0) Complex with an Unsupported Mn–Mg Bond: Allowing Access to Low Coordinate Homo- and Heterobimetallic Compounds
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† School of Chemistry, Monash University, Melbourne, Victoria, 3800, Australia
‡ Department of Chemistry and Minnesota Supercomputing Institute, University of Minnesota 207 Pleasant St, SE Minneapolis, Minnesota 55455-0431,United States
§ School of Chemistry, Cardiff University, Cardiff, CF10 3AT, United Kingdom
J. Am. Chem. Soc., Article ASAP
DOI: 10.1021/ja5021348
Publication Date (Web): March 24, 2014
Copyright © 2014 American Chemical Society
Abstract
This study details the synthesis and characterization of an unprecedented two-coordinate, high-spin manganese(0) complex that incorporates an unsupported Mn–Mg bond, viz. L†MnMg(MesNacnac) (L† = −N(Ar†)(SiPri3), Ar† = C6H2{C(H)Ph2}2Pri-2,6,4; MesNacnac = [(MesNCMe)2CH]−; Mes = mesityl). This compound has been utilized as an “inorganic Grignard reagent” in the preparation of the first two-coordinate manganese(I) dimer, L†MnMnL* (L* = −N(Ar*)(SiMe3), Ar* = C6H2{C(H)Ph2}2Me-2,6,4), and the related mixed valence, bis(amido)-hetereobimetallic complex, MnII(μ-L†)(μ-L*)Cr0. It is also shown to act as a two-electron reducing agent in reactions with unsaturated substrates.
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