Oxidative addition of O 2, Cl 2, NO, NO + and H 2 to [Ru( ν5-C 5Me 5) (Ph 2PCH 2CH 2PPh 2)] + : X-ray structures of [Ru(C1) 2( ν5-C 5Me 5)(Ph 2PCH 2CH 2PPh 2] + and [Ru(NO)( ν5-C 5Me 5)(Ph 2PCH 2CH 2PPh 2] 2+

Abstract

Treatment of Ru( ν 5-C 5Me 5) (dppe)Cl ( 1) (dppe = Ph 2PCH 2CH 2PPh 2) with Ag + (as the PF 6 − or CF 3SO 3 − salt) in CH 3NO 2 as the solvent yields the 16-electron complex [Ru( ν 5-C 5Me 5 (dppe] + ( 2) in quantitative yield. Complex 2 reacts with O 2, Cl 2, NO, NO + and H 2 to form the cationic Ru(IV) complexes [ Ru(ν 5- C 5 Me 5) dppe)] + ( 3), [ Ru( Cl) 2(η 5- C 5 Me 5)( dppe) ] + ( 4), [Ru(NO) ( η 5-C 5Me 5) (dppe)] 2+ ( 5) and [Ru(H) 2( η 5-C 5Me 5)(dppe)] + ( 6) in good yields. The crystal structures of 4b (CF 3SO 3 − salt) and 5b (CF 3SO 3 − salt) have been determined by X-ray diffraction techniques. 4b crystallizes in the triclinic space group P 1 (No. 2), with a=12.215(4), b=12.593(5), c=14.422(4) A ̊ , α=76.45(2), β=79.83(2), gg=84.64(2)°, V=2119.7(12) A ̊ 3, Z=2 . The structure was refined to R( F)=0.0418 ( F≥4 σF). 5b crystallizes in the monoclinic space group P2 1/ n, with a=12.679(4), b=12.269(5), c=27.658(9) A ̊ , β=90.36(1)°, V=4302(3) A ̊ 3, Z=4 . The structure was refined to R( F)=0.0511 ( F≥4 σF).