Preparation of Hydroxylamine and O ‐Methylhydroxylamine Complexes of Manganese and Rhenium

Hydroxylamine and O ‐methylhydroxylamine complexes [M(NH 2 OH)(CO) n P 5– n ]BPh 4 and [M(NH 2 OCH 3 )(CO) n P 5– n ]BPh 4 [M = Mn, Re; n = 1, 2, 3; P = P(OEt) 3 , PPh(OEt) 2 , PPh 2 OEt] were prepared by allowing hydrides MH(CO) n P 5– 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 NH 2 OH and NH 2 OCH 3 complexes of manganese and rhenium of the [M(NH 2 OR)(CO) 2 (P–P)‐{P(OEt) 3 }]BPh 4 and [M(NH 2 OR)(CO) 3 (P–P)]BPh 4 [R = H, CH 3 ; P–P = Ph 2 POCH 2 CH 2 OPPh 2 , Ph 2 PO(CH 2 ) 3 OPPh 2 , Ph 2 PN(CH 3 )CH 2 CH 2 N(CH 3 )PPh 2 ] 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 theX‐ray crystal‐structure determination of [Re(NH 2 OCH 3 )(CO) 2 {PPh(OEt) 2 } 3 ]BPh 4 and [Re(NH 2 OCH 3 )(CO) 3 {Ph 2 PO(CH 2 ) 3 OPPh 2 }]BPh 4 . Oxidation of the hydroxylamine complexes with Pb(OAc) 4 was studied at –40 °C and led to an unstable compound tentatively characterized as a nitroxyl [M]–N(H)=O derivative.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)