Hybrid dibismuthines and distibines as ligands towards transition metal carbonyls

The hybrid dibismuthines O(CH2CH2BiPh2)(2) and MeN(CH2-2-C6H4BiPh2)(2) react with [M(CO)(5)(thf)] (M = Cr or W) to form [{M(CO)(5)}(2){O(CH2CH2BiPh2)(2)}] and [{Cr(CO)(5)}(2){MeN(CH2-2-C6H4BiPh2)(2)}] containing bridging bidentate (Bi-2) coordination. The unsymmetrical tertiary bismuthine complexes [M(CO)(5){BiPh2(o-C6H4OMe)}] are also described. Depending upon the molar ratio, the hybrid distibines O(CH2CH2SbMe2)(2) and MeN(CH2-2-C6H4SbMe2)(2) react with [M(CO)(5)(thf)] to give the pentacarbonyl complexes [{M(CO)(5)}(2){O(CH2CH2SbMe2)(2)}] and [{Cr(CO)(5)}(2){MeN(CH2-2-C6H4SbMe2)(2)}] or tetracarbonyls cis-[M(CO)(4){O(CH2CH2SbMe2)(2)}] and cis-[M(CO)(4){MeN(CH2-2-C6H4SbMe2)(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(CH2-2-C6H4SbMe2)(2) coordinates as a tridentate (SSb2) in fac-[M(CO)(3){S(CH2-2-C6H4SbMe2)(2)}] (M = Cr or Mo) and fac-[Mn(CO)(3){S(CH2-2-C6H4SbMe2)(2)}][CF3SO3]. Fac-[Mn(CO)(3){MeN(CH2-2-C6H4SbMe2)(2)}][CF3SO3] contains NSb2-coordinated ligand in the solid state, but in solution a second species, Sb2-coordinated and with a kappa(1)-CF3SO3 replacing the coordinated amine is also evident. X-ray crystal structures were also determined for fac-[Cr(CO)(3){S(CH2-2-C6H4SbMe2)(2)}], fac-[Mn(CO)(3){S(CH2-2-C6H4SbMe2)(2)}][CF3SO3] and fac-[Mn(CO)(3){MeN(CH2-2-C6H4SbMe2)(2)}] [CF3SO3]. Hypervalent N center dot center dot center dot Sb interactions are present in cis-[M(CO)(4){MeN(CH2-2-C6H4SbMe2)(2)}] (M = Mo or W), but absent for M = Cr.