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Facile C–N bond cleavage mediated by electron-rich cyclopentadienyl cobalt(I) complexes by Helmut Werner; Gerhard Hörlin; William D Jones is a Chemistry article available to read on EtoBox.

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The reaction of [C 5 H 5 Co(PMe 3 ) 2 ] (1) with one equiv of CNCH 2 Ph leads to the formation of the substitution product [C 5 H 5 Co(CNCH 2 Ph)(PMe 3 )] (2) which even at room temperature undergoes an intramolecular oxidative addition to give the isomer [C 5 H 5 Co(CN)(CH 2 Ph)(PMe 3 )] (4). The corresponding Cp\*Co derivative [C 5 Me 5 Co(CN)(CH 2 Ph)(PMe 3 )] ( 8) is obtained from [C 5 Me 5 Co(PMe 3 ) 2 ] (5) and CNCH 2 Ph. In contrast to 2, the analogous compound [C 5 H 5 Co(CNTol)(PMe 3 )] ( 6) is quite inert and does not react by N-C bond cleavage. The conversion of 2 to 4 in C 6 D 6 , acteone-d 6 and methanol-d 4 follows first order kinetics with a rate that is almost independent of the concentration of free PMe 3 . Both 2 and 6 react with Ph 2 CN 2 to give the C,C-bound ketenimine complexes [C 5 H 5 Co(s 2 -C,C-Ph 2 C C NR)(PMe 3 )] (9, 10) of which that with R = Tol rearranges thermally to the more stable N,C-bound isomer 11.

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Author

Helmut Werner; Gerhard Hörlin; William D Jones

Publisher

Elsevier Science; Elsevier ; Elsevier BV (ISSN 0022-328X)

Published

1998

Language

EN

Field

Chemistry (Physical Sciences)