Synthesis of new (cyclopentadienyl)rutheniumphosphine complexes with hemilabile ether-phosphines. The X-ray structure of (η 5-C 5H 5)RuCl(Ph 2PCH 2CH 2OCH 3) 2

Abstract

The reaction of CpRuCl(PPh 3) 2 (Cp=η 5-C 5H 5) with excess ether-phosphine ligand (O,P=Ph 2PR, where R is ether containing alkyl chain) in toluene or n-heptane leads to the mixed complexes CpRuCl(PPh 3)(P∼O) 2 and/ or the bis(ether-phosphine) complexes CpRuCl(P∼O) 2. A single X-ray structure determination has been carried out for CpRuCl(Ph 2PCH 2CH 2OCH 3) 2 ( 4a): space group P 1 , a=9.2806(6), b=11.9454(8), c=15.2216(9) Å, α=84.482(9), β=74.592(5), γ=85.066(8)°, V= 1616.1(3) Å 3, F(000)=712, D x=1.42 g cm −3, Z=2, R=0.064, R w=0.075. Treatment of 4a with AgSbF 6 affords the salt [CpRu( PO )(P∼O)][SbF 6] ( 5a), with one mono- (P∼O) and one bidentate coordinating ( PO ) ether-phosphine ligand. The fluxional behaviour of the cation of 5a has been studied by temperature dependent 31p{ 1H} NMR investigations. Stirring 5a under an atmosphere of carbon monoxide resulted in the formation of [CpRu(P∼O) 2(CO)][SbF 6] ( 6a). All complexes have been characterized by 1H, 31P{ 1H}, 13C{ 1H} NMR, IR, mass spectroscopy and elemental analysis.