TY - JOUR
T1 - Cyclo-oligomerisation reactions of bis(alkyne) and η2-vinyl complexes of molybdenum and tungsten with t-butyl isocyanide leading to iminocyclo-pentadiene derivatives
AU - Davidson, Jack L.
AU - Wilson, William F.
PY - 1988
Y1 - 1988
N2 - Reactions of t-butyl isocyanide with bis(alkyne) complexes [M(SR)(CF3C=CCF3)2(? 5-C5H5)] (M = Mo, R = C6F5; M = W, R = C6H4Me-4) and isomeric ?2-vinyl complexes [W{C(CF3)C(CF3)SR}(CF3C=CCF 3)(?5-C5H5)] (R = Me, Pri, or But) give bis(isocyanide)-metallacyclic derivatives [M{C(CF3)=C(CF3)C(CF3)=C(CF 3)}(SR)(CNBut)2(?5-C 5H5)] (7), via ?2-vinyl, [M{?2-C(CF3)C(CF3)CNBu t}(SR)(CF3C=CCF3)(? 5-C5H5)] (M = Mo, R = C6F5), or 16-electron monoisocyanide complexes, [W{C(CF3)=C(CF3)C(CF3)=C(CF 3)}(SR)(CNBut)(?5-C5H 5)] (6), isolated for M = W, R = But. Metallacyclic complexes (6) (R = But) and (7) (M = W; R = C6H4Me-4, Pri, or But) can be hydrolysed to the iminoacyl oxo complex [W{?3-C(NBut)C(CF3)=C(CF 3)C(CF3)=C(CF3)H}(O)(?5-C 5H5)] whereas thermolysis of (7) (M = Mo, R = C6F5; M = W, R = Pri) gives complexes [M(SR)(CNBut){?2-C4(CF3) 4CNBut}(?5-C5H5)] containing an iminocyclopentadiene ligand bonded in a novel ?2 manner via the exocyclic C-N bond to the metal.
AB - Reactions of t-butyl isocyanide with bis(alkyne) complexes [M(SR)(CF3C=CCF3)2(? 5-C5H5)] (M = Mo, R = C6F5; M = W, R = C6H4Me-4) and isomeric ?2-vinyl complexes [W{C(CF3)C(CF3)SR}(CF3C=CCF 3)(?5-C5H5)] (R = Me, Pri, or But) give bis(isocyanide)-metallacyclic derivatives [M{C(CF3)=C(CF3)C(CF3)=C(CF 3)}(SR)(CNBut)2(?5-C 5H5)] (7), via ?2-vinyl, [M{?2-C(CF3)C(CF3)CNBu t}(SR)(CF3C=CCF3)(? 5-C5H5)] (M = Mo, R = C6F5), or 16-electron monoisocyanide complexes, [W{C(CF3)=C(CF3)C(CF3)=C(CF 3)}(SR)(CNBut)(?5-C5H 5)] (6), isolated for M = W, R = But. Metallacyclic complexes (6) (R = But) and (7) (M = W; R = C6H4Me-4, Pri, or But) can be hydrolysed to the iminoacyl oxo complex [W{?3-C(NBut)C(CF3)=C(CF 3)C(CF3)=C(CF3)H}(O)(?5-C 5H5)] whereas thermolysis of (7) (M = Mo, R = C6F5; M = W, R = Pri) gives complexes [M(SR)(CNBut){?2-C4(CF3) 4CNBut}(?5-C5H5)] containing an iminocyclopentadiene ligand bonded in a novel ?2 manner via the exocyclic C-N bond to the metal.
UR - http://www.scopus.com/inward/record.url?scp=37049089352&partnerID=8YFLogxK
U2 - 10.1039/DT9880000027
DO - 10.1039/DT9880000027
M3 - Article
SN - 1472-7773
SP - 27
EP - 34
JO - Journal of the Chemical Society, Dalton Transactions
JF - Journal of the Chemical Society, Dalton Transactions
IS - 1
ER -