Preparation of hydroxylamine and O-methylhydroxylamine complexes of manganese and rhenium

摘要

Hydroxylamine and O-methylhydroxylamine complexes [M(NH2OH)(CO)(n)P5-n]BPh4 and [M(NH2OCH3)(CO)(n)P5-n]BPh4 [M = Mn, Re; n = 1, 2, 3; P = P(OEt)(3), PPh(OEt)(2), PPh2OEt] were prepared by allowing hydrides MH(CO)(n)P5-n to react first with triflic acid and then with an excess of hydroxylamine. Bidentate phosphane and phosphite can also be used to prepare both NH2OH and NH2OCH3 complexes of manganese and rhenium of the [M(NH2OR)(CO)(2)(P-P){P(OEt)(3)}]BPh4 and [M(NH2OR)(CO)(3)(P-P)]BPh4 [R = H, CH3; P-P = Ph2POCH2CH2OPPh2, Ph2PO(CH2)(3)OPPh2, Ph2PN(CH3)CH,CH2N(CH3)PPh2] types with the use of MH(CO)(2)- (P-P){P(OEt)(3)} and MH(CO)(3)(P-P) as precursors. The complexes were characterized spectroscopically and by the X-ray crystal-structure determination of [Re(NH2OCH3)(CO)(2){PPh(OEt)(2)}(3)]BPh4 and [Re(NH2OCH3)(CO)(3){Ph2PO(CH2)(3)OPPh2}]BPh4. Oxidation of the hydroxylamine complexes with Pb(OAc)(4) was studied at -40 degrees C and led to an unstable compound tentatively characterized as a nitroxyl [M]N(H)=O derivative. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)