Hybrid dibismuthines and distibines as ligands towards transition metal carbonyls

The hybrid dibismuthines O(CH(2)CH(2)BiPh(2))(2) and MeN(CH(2)-2-C(6)H(4)BiPh(2))(2) react with M(CO)(5)(thf)] (M = Cr or W) to form {M(CO)(5)}(2){O(CH(2)CH(2)BiPh(2))(2)}] and {Cr(CO)(5)}(2){MeN(CH(2)-2-C(6)H(4)BiPh(2))(2)}] containing bridging bidentate (Bi(2)) coordination. The unsymmetrical tertiary bismuthine complexes M(CO)(5){BiPh(2)(o-C(6)H(4)OMe)}] are also described. Depending upon the molar ratio, the hybrid distibines O(CH(2)CH(2)SbMe(2))(2) and MeN(CH(2)-2-C(6)H(4)SbMe(2))(2) react with M(CO)(5)(thf)] to give the pentacarbonyl complexes {M(CO)(5)}(2){O(CH(2)CH(2)SbMe(2))(2)}] and {Cr(CO)(5)}(2){MeN(CH(2)-2-C(6)H(4)SbMe(2))(2)}] or tetracarbonyls cis-M(CO)(4){O(CH(2)CH(2)SbMe(2))(2)}] and cis-M(CO)(4){MeN(CH(2)-2-C(6)H(4)SbMe(2))(2)}]. The latter can also be obtained from Cr(CO)(4)(nbd)] or W(CO)(4)(pip)(2)], and contain chelating bidentates (Sb(2)-coordinated) as determined crystallographically. S(CH(2)-2-C(6)H(4)SbMe(2))(2) coordinates as a tridentate (SSb(2)) in fac-M(CO)(3){S(CH(2)-2-C(6)H(4)SbMe(2))(2)}] (M = Cr or Mo) and fac-Mn(CO)(3){S(CH(2)-2-C(6)H(4)SbMe(2))(2)}]CF(3)SO(3)]. Fac-Mn(CO)(3){MeN(CH(2)-2-C(6)H(4)SbMe(2))(2)}]CF(3)SO(3)] contains NSb(2)-coordinated ligand in the solid state, but in solution a second species, Sb(2)-coordinated and with a κ(1)-CF(3)SO(3) replacing the coordinated amine is also evident. X-ray crystal structures were also determined for fac-Cr(CO)(3){S(CH(2)-2-C(6)H(4)SbMe(2))(2)}], fac-Mn(CO)(3){S(CH(2)-2-C(6)H(4)SbMe(2))(2)}]CF(3)SO(3)] and fac-Mn(CO)(3){MeN(CH(2)-2-C(6)H(4)SbMe(2))(2)}] CF(3)SO(3)]. Hypervalent N···Sb interactions are present in cis-M(CO)(4){MeN(CH(2)-2-C(6)H(4)SbMe(2))(2)}] (M = Mo or W), but absent for M = Cr.