TY - JOUR
T1 - Co-ordinatively unsaturated alkyne complexes of molybdenum and tungsten. Reactions of [MCl(CF3C=CCF3)2(η-C5H 5)] (M = Mo or W) with heterocyclic thiolates leading to η2-vinyl complexes
AU - Davidson, Jack L.
AU - Murray, I. E P
AU - Preston, Peter N.
AU - Russo, Maria V.
PY - 1983
Y1 - 1983
N2 - Reactions of Tl(SR) (SR- = pyridine-2-thiolate, pyrimidine-2-thiolate, or thiazoline-2-thiolate) with the bis(hexafluorobut-2-yne) complex [MoCl(CF3C=CCF3)2(?-C5H 5)] give products [Mo{C(CF3)-C(CF3)RS}(CF3C=-CCF 3)(?-C5H5)] containing a novel ?2-vinyl ligand resulting from nucleophilic attack of nitrogen on a co-ordinated alkyne. The same pyridine-2-thiolate complex is obtained from the reaction of [MoCl(CF3C=CCF3)2(?-C5H 5)] with the thallium(I) salt of 2-mercaptopyridine N-oxide, in addition to [Mo{C(CF3)=C(CF3)C(CF3)=C(CF 3)SC5H4NO}(?-C5H5)]. The complex [WCl(CF3C=CCF3)2(?-C5H 5)] reacts with thallium(I) pyridine-2-thiolate to give the ?2-vinyl complex [W{C(CF3)-C(CF3)NC5H4S}(CF 3C=CCF3)(?-C5H5)], whereas with Tl(SC5H4NO) cyclopentadienyl-ligand displacement is also observed giving the co-ordinatively unsaturated bis(hexafluorobut-2-yne) complexes [W(SC5H4NO)2(CF3C=CCF 3)2] and [W(SC5H4N) (SC5H4NO)(CF3C=CCF3)2].
AB - Reactions of Tl(SR) (SR- = pyridine-2-thiolate, pyrimidine-2-thiolate, or thiazoline-2-thiolate) with the bis(hexafluorobut-2-yne) complex [MoCl(CF3C=CCF3)2(?-C5H 5)] give products [Mo{C(CF3)-C(CF3)RS}(CF3C=-CCF 3)(?-C5H5)] containing a novel ?2-vinyl ligand resulting from nucleophilic attack of nitrogen on a co-ordinated alkyne. The same pyridine-2-thiolate complex is obtained from the reaction of [MoCl(CF3C=CCF3)2(?-C5H 5)] with the thallium(I) salt of 2-mercaptopyridine N-oxide, in addition to [Mo{C(CF3)=C(CF3)C(CF3)=C(CF 3)SC5H4NO}(?-C5H5)]. The complex [WCl(CF3C=CCF3)2(?-C5H 5)] reacts with thallium(I) pyridine-2-thiolate to give the ?2-vinyl complex [W{C(CF3)-C(CF3)NC5H4S}(CF 3C=CCF3)(?-C5H5)], whereas with Tl(SC5H4NO) cyclopentadienyl-ligand displacement is also observed giving the co-ordinatively unsaturated bis(hexafluorobut-2-yne) complexes [W(SC5H4NO)2(CF3C=CCF 3)2] and [W(SC5H4N) (SC5H4NO)(CF3C=CCF3)2].
UR - http://www.scopus.com/inward/record.url?scp=37049104569&partnerID=8YFLogxK
U2 - 10.1039/DT9830001783
DO - 10.1039/DT9830001783
M3 - Article
SN - 1472-7773
SP - 1783
EP - 1787
JO - Journal of the Chemical Society, Dalton Transactions
JF - Journal of the Chemical Society, Dalton Transactions
IS - 8
ER -