Molybdenum(0) Dihapto-Coordination of Benzene and Trifluorotoluene: The Stabilizing and Chemo-Directing Influence of a CF3 Group

• DOI: 10.1021/jacs.7b05009
• Publication Date: 2017-07-25T21:39:32Z
• Authors: Jeffery T. Myers; Jacob A. Smith; Steven J. Dakermanji; Justin H. Wilde; Katy B. Wilson; Philip J. Shivoke...; W. Dean Harman
• Keywords: 01 natural sciences; 0104 chemical sciences

The preparation of the complexes TpMo(NO)(DMAP)(η2-PhCF3) (5) and TpMo(NO)(DMAP)(η2-benzene) (3) is described. CF3 group found to stabilize metal–arene bond strength in 5 by roughly 3 kcal/mol compared that 3, allowing large-scale synthesis isolation trifluorotoluene analogue (5, 37 g, 70%). When a benzene solution allowed stand, clean conversion occurs, this complex may be precipitated from upon addition pentane isolated. shown synthetic precursor functionalized cyclohexadienes: In solution, it selectively protonates at ortho position, resulting η2-arenium species undergoes reactions with nucleophiles adjacent meta carbon. Thus, 5, triflic acid, either N-methylpyrrole or 1-methoxy-2-methyl-1-(trimethylsilyloxy)-1-propene result 5-substituted-1,3-cyclohexadienes after removal metal.