M. Al-jahdali et al., Use of the seven-coordinate complexes [MXY(CO)(3)(NCMe)(2)] (M = Mo or W; X, Y = halide) and their derivatives in homogeneous catalysis, J MOL CAT A, 159(1), 2000, pp. 51-62
The seven-coordinate halocarbonyl complexes, [MXY(CO)(3)(NCMe)(2)] (M = Mo
or W; X, Y = halide) and their derivatives have been investigated in severa
l types of homogeneous catalytic reactions. These include, the alkene metat
hesis polymerisation of norbornadiene using either, [MX2(CO)(3)(NCMe)(2)] (
M = Mo or W; X = Br or I), [MI2(CO)(3)(L'-P, P')] {M = Mo or W; L' = MeC(CH
2PPh2)(3)} or [MXY(CO)(L or L'-P, P')(eta(2)-RC2R')] {X,Y = Cl, Br or I; L
= PhP(CH2CH2PPh2)(2); R,R' = Me, Ph). The isolation and characterisation of
a key intermediate, [WI2(CO)(2)(eta(4)-nbd)] (1) (nbd = norbornadiene) is
also described. The development of water soluble polymerisation catalysts u
sing water-solubilising pyridine ligands, and the biphasic polymerisation o
f styrene using [WI2(CO)(3)(NC5H4CO2Na-4)(2)], ZrCl4, sodium lauryl sulphat
e and sodium hydrogen phosphate is also discussed. The room temperature pol
ymerisation of phenylacetylene using [WX2(CO)(3)(NCMe)(2)] (X = Cl, I), [WI
2(CO)(3)(NCMe)L] (L = PPh3, AsPh3) or [WBr2(CO)(NCMe)(eta(2)-HC2Ph)(2)] (4)
is also described, and a mechanism is proposed for these polymerisation re
actions. (C) 2000 Elsevier Science B.V. All rights reserved.