Substitution reactions of cis-bis(2,2′-bipyridine)dicarbonyl(solvent)molybdenum(II) and cis-bis(2,2′-bipyridine)dicarbonyltungsten(II) salts with uni-, bi-, and ter-dentate tertiary phosphines, trimethyl phosphite, nitric oxide, and 2,2′-bipyridine
Abstract
Reaction of cis-[Mo(CO)2(bipy)2(NCMe)][BF4]2(bipy = 2,2′-bipyridine) with PPh3 and PBun3 substitutes the solvent to produce [Mo(CO)2(bipy)2(PR3)][BF4]2(R = Ph or Bun) under mild conditions. Oxidation of cis-[Mo(CO)2(bipy)2] with Ag[BF4] in trimethyl phosphite at room temperature gives [Mo(CO)2(bipy)2{P(OMe)3}][BF4]2. Under similar conditions, further substitution of one carbonyl ligand, to give [Mo(CO)(bipy)2L2][BF4]2[L = PEt3 or P(OMe)3], or both carbonyl ligands to give [Mo(NO)2(bipy)2][BF4]2 or [Mo(bipy)3][BF4]2 may occur. Reaction of cis-[W(CO)2(bipy)2][BF4]2 with the same phosphorus donor ligands results in the substitution of bipy to form cis-[W(CO)2(bipy)L2][BF4]2[L = PPh3 or P(OMe)3]; reaction with bis(diphenylphosphino)methane (dppm) or 1,2-bis(diphenylphosphino)ethane (dppe) produces [WF(CO)2(bipy)(L–L)][BF4](L–L = dppm or dppe). Reaction of [Mo(CO)2(bipy)2(NCMe)][BF4]2 with dppe produces [Mo(CO)(bipy)2(dppe)][BF4]2. With bis(2-diphenylphosphinoethyl)phenylphosphine (bdpp), cis[W(CO)2(bipy)2][BF4]2 forms [W(CO)2(bipy)(bdpp)][BF4]2 in high yield. The new complexes have been characterised by microanalysis, spectroscopy (i.r., 1H, 13C, 19F, 31P n.m.r., electronic absorption), and conductivity measurements. [Mo(NO)2(bipy)2][BF4]2 reacts with Na[S2CNEt2] to give [Mo(NO)2(S2CNEt2)2].
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