Coordinated 2-halo-1,3,2-dioxaphosphorinane ligands. III. cis-Mo(CO)42 (E = O, S, NH; R = alkyl, aryl or ER = Cl, Br) complexes: syntheses, spectroscopic studies and the molecular structures of the cis-Mo(CO)4iPrEP(OCH2CMe2CH2O)>2 (E = O, NH) complexes

Article abstract of DOI:10.1016/0022-328X(92)83305-2

A study of the reactions of cis-Mo(CO)4(XP(OCH2CMe2CH2O)>2 (X = Cl, Br) complexes with a variety of nucleophiles of the type HER (E = NH, O, S; R = H, alkyl, aryl) is reported.The 13C, 31P and 95 Mo NMR and IR data for the cis-Mo(CO)4(REP(OCH2CMe2CH2O)>2 complexes are presented and compared to those previously reported for some Mo(CO)5(REP(OCH2CMe2CH2O)> and cis-Mo(CO)4(Ph2PER)2 complexes.This comparison demonstrates that the effects of variations in the RE substituents in these complexes are similar to those previously observed for the Mo(CO)5)> complexes.The X-ray crystal structures of cis-Mo(CO)4<ⁱPrOP(OCH2CMe2CH2O)>2 (triclinic space group P<*>; a = 8.818(3), b = 8.899(1). c = 18.847(2) Angstroem; α = 93.35(1), β = 89.46(2), γ = 115.31(1) deg; V = 1334.6(4) Angstroem³; Z = 2) and cis-Mo(CO)4<ⁱPrNHP(OCH2CMe2CH2O)>2 (monoclinic space group C2/c; a = 18.30(1), b =10.72(2), c = 16.87(1) Angstroem; β = 119.82(5) deg; V = 2871(4) Angstroem³; Z = 4) have also been determined.In these complexes, the OⁱPr group is in an axial position, but the NHⁱPr group is in an equatorial position.