| Popis: |
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 the X-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. |
