Preparation of Hydroxylamine Complexes of Ruthenium( II ), Osmium( II ) and Iridium( III )

The hydroxylamine complexes [MH(NH 2 OH)P 4 ]BPh 4 (M = Ru, Os) and [Ru(NH 2 OH) 2 P 4 ](BPh 4 ) 2 [P = P(OEt) 3 , PPh(OEt) 2 ] were prepared by allowing the triflate species MH(κ 1 ‐OSO 2 CF 3 )P 4 and [Ru(κ 2 ‐O 2 SOCF 3 )P 4 ] + to react with an excess of hydroxylamine. The iridium complexes [IrCl 2 (NH 2 OH)PL 2 ]BPh 4 [P = P(OEt) 3 , PPh(OEt) 2 ; L = PPh 3 , AsPh 3 ] and [IrH 2 (NH 2 OH)(PPh 3 ) 3 ]BPh 4 were also prepared by reacting the hydride species [IrHCl 2 PL 3 ] and [IrH 3 (PPh 3 ) 3 ] first with triflic acid and then with an excess of NH 2 OH. The O ‐iminoacylated hydroxylamine complexes [M{η 2 ‐NH=C(R)ONH 2 }P 4 ](BPh 4 ) 2 and [M{η 2 ‐NH=C(R)ONH(CH 3 )}P 4 ](BPh 4 ) 2 (M = Ru, Os; R = CH 3 , 4‐CH 3 C 6 H 4 ) were prepared by allowing the nitrile complexes [M(RCN) 2 P 4 ](BPh 4 ) 2 to react with hydroxylamine (NH 2 OH) or N ‐methylhydroxylamine [NH(CH 3 )OH]. The compounds were characterised spectroscopically (IR, 1 H, 13 C and 31 P NMR) and a geometry in solution was also established. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)