Structural tungsten-imido chemistry: the gas-phase structure of W(NBut)2(NHBut)2 and the solid-state structures of novel heterobimetallic W/N/M (M = Rh, Pd, Zn) species.
The gas-phase (electron diffraction) and solid-state (X-ray) structures of W(NBut)2(NHBut)2 (1) have been determined. In the gas phase, 1 adopts both C1 and C2 conformations in a 69:31 ratio. The solid-state structure is disordered over two equal sites, both showing approximate C2 conformation as in the gas phase; the imido and amido centers are, however, clearly distinguished. Compound 1 has been used to synthesize novel heterobimetallic derivatives W(NBut)4[Rh(COD)]2 (3) and W(NBut)4[Pd(eta3-C3H5)]2 (4) via the dilithiated intermediate Li2[W(NBut)4] (2). In both cases, the [W(NBut)4] moiety bridges the two organometallic fragments. Reaction of 1 with Me2Zn has produced [Me(tBuN)W(mu-NBut)2ZnMe(NH2But)] (5). The structures of 3, 4, and 5 have been determined. Thermal decomposition of 4 under an autogenerated pressure at 700 degrees C has formed the hitherto uncharacterized bimetallic alloy WPd2.
Choujaa
Hamid
H
Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, United Kingdom.
Cosham
Samuel D
SD
Johnson
Andrew L
AL
Kafka
Graeme R
GR
Mahon
Mary F
MF
Masters
Sarah L
SL
Molloy
Kieran C
KC
Rankin
David W H
DW
Robertson
Heather E
HE
Wann
Derek A
DA