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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
Authors:Fritz Näumann  Dieter Rehder
Affiliation:Institut für Anorganische und Angewandte Chemie der Universität Hamburg, Martin-Luther-King-Platz 6, D-2000 Hamburg 13 F.R.G.
Abstract:η5-C5H5V(NO)2CO is prepared in 40% yield by the photo-reaction between η5-C5H5V(CO)4 and [Co(NO)2Br]25-C5H5V(NO)2CO reacts by an SN1 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, BUt) as the cone angle of PR3increases.
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