Synthesis, crystal structure, and reactions of the 17-valence-electron rhenium methyl complex [(η5-C5Me5)Re(NO)(P(4-C6H 4CH3)3)(CH3)]•+ B(3,5-C6H3(CF3)2)-4: Academic Article uri icon

abstract

  • Reactions of methyl complex (η5-C5Me5)Re(NO)(P(4-C6H 4CH3)3)(CH3) (2b) and the ferrocenium salt (η5-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 [(η5-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 (ΔG‡383K > 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.

altmetric score

  • 3

author list (cited authors)

  • Le Bras, J., Jiao, H., Meyer, W. E., Hampel, F., & Gladysz, J. A.

citation count

  • 29

publication date

  • December 2000