Synthesis and reactivity of functionalized rhenium phosphido complexes (.eta.5-C5H5)Re(NO)(PPh3)(PXX'): an unusual carbon tetrachloride 1,3-addition leading to an exo-substituted .eta.4-cyclopentadiene complex
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Reaction of the phenylphosphido complex (η5-C5 H5)Re(NO)(PPh3)(PPhH) and CCl4(1 equiv, -98 °C) gives the labile chloro-phenylphosphido complex (η5-C5 H5)Re(NO)(PPh3)(PPhCl) (2, mixture of diastereomers), which is characterized in situ by NMR spectroscopy and methylation to the isolable bis(phosphine) complex [(η5-C5 H5)Re(NO)(PPh3)(PPhMeCl)]+ I-. Reaction of P(NMe2)3 and either 2 (1.0 equiv) or the dichlorophenylphosphine complex [(η5-C5 H5)Re(NO)(PPh3)(PPhCl2)]+ CF3 S03-(0.5 equiv) gives predominantly [(η5-C5 H5)Re(NO)(PPh3)(PPh(P(NMe2)2))]+ Cr, which is characterized in situ by NMR spectroscopy. Reaction of Li+[(η5-C5 Hs)Re(NO)(PFh3)]- with t -bupc 12 and P(OPh)3 gives (η5-C5 H5)Re(NO)(PPh3)(P(t-Bu)Cl) (9, 72%) and (η5-C5 H5)Re(NO)(PPh3)(P(OPh)2) (10, 57%), respectively. Reaction of 2 and CCl4 gives the η4-cyclopentadiene complex (η4-C5 H5 CCl3)Re(NO)(PPh3)(PPhCl2), which exhibits dynamic NMR behavior and is characterized by an X-ray crystal structure (monoclinic, P21/c, a = 9.352 (2) Å, b = 31.241 (8) Å, c = 10.812 (1) Å, β = 102.54 (1)°, Z = 4). Reactions of 2, 9, and 10 with potential halide abstractors and related reagents are also described. © 1989, American Chemical Society. All rights reserved.
author list (cited authors)
Buhro, W. E., Arif, A. M., & Gladysz, J. A.