Transition metal nitrosyls as nitrosylation agents : II.Photo-nitrosylation of η5-C5H5V(CO)3L(L = CO, Pz3) by [Co(NO)2Br]2

doi:10.1016/S0022-328X(00)80510-0

Journal of Organometallic Chemistry

Volume 204, Issue 3, 20 January 1981, Pages 411-414

https://doi.org/10.1016/S0022-328X(00)80510-0 Get rights and content

Abstract

η⁵-C₅H₅V(NO)₂CO is prepared in 40% yield by the photo-reaction between η⁵-C₅H₅V(CO)₄ and [Co(NO)₂Br]₂.η⁵-C₅H₅V(NO)₂CO reacts by an S_N1 mechanism with various phosphines PZ₃ to yield η⁵-C₅-H₅V(NO)₂PZ₃. The phosphine complexes are also obtained by photo-induced ligand interchange between η⁵-C₅H₅V(CO)₃PZ₃ and [Co(NO)₂Br]₂, or η⁵-C₅H₅V(CO)₄ and Co(NO)₂Br(PZ₃). In all cases, the main cobalt species formed is Co(NO)(CO)₃. While the one-bond vanadiumphosphorus coupling constants of most of the phosphine complexes are virtually the same (ca 410 Hz),the chemical shift values δ(⁵¹V) (−1328 to −973 ppm rel. VOCl₃) decrease in the order PF₃ > CO > P(OR)₃ > P(alkyl)₃ > PPh₃ > PPh(NEt₂)₂, reflecting the decreasing π-acceptor ability of the ligands. δ(⁵¹V) also decreases in the series of alkylphosphines PR₃ (R = Me, Et, Prⁿ, Buⁱ, Prⁱ, BU^t) as the cone angle of PR₃increases.

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^☆: See ref. 9 for communication.

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Transition metal nitrosyls as nitrosylation agents : II.Photo-nitrosylation of η5-C5H5V(CO)3L(L = CO, Pz3) by [Co(NO)2Br]2☆

Abstract

Inorg. Chim. Acta

J. Organometal. Chem.

J. Magn. Reson.

J. Inorg. Nucl. Chem.

J. Magn. Reson.

J. Amer. Chem. Soc.

Inorg. Chem.

Inorg. Chem.

Inorg. Chem.

J. Organometal. Chem.

Z. Anorg. Allgem. Chem.

Transition metal nitrosyls as nitrosylation agents : II.Photo-nitrosylation of η⁵-C₅H₅V(CO)₃L(L = CO, Pz₃) by [Co(NO)₂Br]₂☆