Synthesis of Bis{(2-dimethylphosphino)ethane-1-thiolato}bis(tert-butylthiolato)- molybdenum(IV) and Its Cluster-Forming Reactions with FeCl(2) and CuBr.
Reaction of Mo(S(t)Bu)(4) with 2 equiv of HSCH(2)CH(2)PMe(2) (Hdmsp) produced Mo(dmsp)(2)(S(t)Bu)(2) (1) in high yield. Treatment of 1 with FeCl(2) and CuBr led to the formation of heterometallic clusters, [Mo(O)(dmsp)(2)](2)FeCl(2) (2) and [MoBr(dmsp)(2)(&mgr;(3)-S)Cu(2)](2)(&mgr;(2)-S(t)Bu)(2) (3), respectively. The structures of 1-3 were determined by X-ray analyses. Complex 1 assumes a distorted octahedral geometry with a cis-disposition of two (t)BuS ligands. In the structure of 2, an FeCl(2) unit bridges two square-pyramidal Mo(O)(dmsp)(2) fragments through interactions between Fe and dmsp sulfur atoms, where the MoS(2)Fe quadrilateral is puckered. Formation of 3 involves C-S bond cleavage of one (t)BuS ligand of 1 and rearrangement of ligands between the Mo and Cu coordination sites, resulting in the structure consisting of two MoCu(2)BrS(dmsp)(2) cluster units and two (t)BuS bridges.
Arikawa
Yasuhiro
Y
Research Center for Materials Science and Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan.
Kawaguchi
Hiroyuki
H
Kashiwabara
Kazuo
K
Tatsumi
Kazuyuki
K