Synthesis, crystal structure, and reactions of the 17-valence-electron rhenium methyl complex [(5-C5Me5)Re(NO)(P(4-C6H 4CH3)3)(CH3)]+ B(3,5-C6H3(CF3)2)-4:
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Reactions of methyl complex (5-C5Me5)Re(NO)(P(4-C6H 4CH3)3)(CH3) (2b) and the ferrocenium salt (5-C5H5)2Fe+ BAr-F (BAr-F = B(3,5-C6H3(CF3)2)-4) or the trityl salt Ph3C+ BAr-F; give the very air sensitive title radical cation 2b+ BAr-F or the robust methylidene complex [(5-C5Me5)Re(NO)(P(4-C6H 4CH3)3)(=CH2)]+ BAr-F (3b+ BAr-F) as analytically pure powders in 80% yields. The crystal structures of 2b and 2b+ BAr-F are determined. With the aid of high level density functional calculations on model complexes, key structural, bonding, and dynamic properties are compared. Similar quantities are calculated for 3b+ BAr-F, which could not be crystallized, and the Re=CH2 rotational barrier is bounded by NMR (G383K > 17.5 kcal mol-1). Special attention is given to structural manifestations of backbonding, particularly with the phosphine ligands. Cobaltocene and 2b+ BAr-F react to give 2b. However, no phosphine exchange or well-defined thermal decomposition products of 2b+ BAr-F are detected. 2000 Elsevier Science B.V. All rights reserved.
