Mono and bimetallic complexes of molybdenum(II) and tungsten(II) containing 4,4′-diphenylenecarbonitrile

The complexes [MI2(CO)(3)(NCMe)(2)] (M = Mo or W) react in CH2Cl2 at room temperature with two equivalents of 4,4'-diphenylenecarbonitrile (dpc) to afford the new seven-coordinate complexes, [MI2(CO)(3)(4,4'-dpc-N)(2)] (1 and 2) in good yield. Equimolar quantities of [MI2(CO)(3)(NCMe)(2)] and PPh3 give [MI2(CO)(3)(NCMe)(PPh3)], which react in situ with 4,4'-dpc to yield the mono-4,4'-diphenylenecarbonitrile complexes, [MI2(CO)(3)(4,4'-dpc-N)(PPh3)] (3 and 4). Treatment of the bis(alkyne) complexes, [WI2(CO)(NCMe)(eta(2) -RC2R)(2)] (R = Me and Ph) with one equivalent of 4,4'-dpc in CH2Cl2 at room temperature affords the acetonitrile displaced products, [WI2(CO)(4,4'-dpc-N)(eta(2) -RC2R)(2)] (5 and 6). Reaction of equimolar quantities Of [WI2(CO)(NCMe)(eta(2)-PhC2Ph)(2)] and 2 in CH2Cl2 at room temperature gives the 4,4'-dpc-bridged complex, [WI2(CO){WI2(CO)(3)(4,4'-dpc-N)(4,4'-dpc-NN'))(eta(2) -PhC2Ph)(2)] (7) in good yield. Similarly, equimolar amounts Of [WI2(CO)(NCMe)(eta(2) -RC2R)(2)] (R = Me and Ph) and (4) react in CH2Cl2 to afford the bimetallic complexes, [WI2(CO){WI2(CO)(4,4'-dpc-N,N')(PPh3)}(eta(2)-RC2R)(2)] (8 and 9). The new bimetallic 4,4'-dpc-bridged alkyne complexes, [WI2(CO)[WI2(CO)(4,4'-dpc-N,N')(eta(2)-MCC2Me)(2)}(eta(2)-MeC2Me)(2)] [(10), [WI2(CO){WI2(CO)(4,4'-dpe-N,N')(eta(2)-PhC2Ph)(2)}eta(2)-PhC2Ph)(2)] (11) and [WI2(CO){WI2(CO)(4,4'-dpc-N,N')(eta(2)-MeC2Me)(2)}(eta(2)-PhC2Ph)(2)] (12) are also described.