Synthesis and Reactivity of the Ruthenium(II) Dihydride Ru(Ph2PNMeNMePPh2)2H2

The reaction of air-stable RuCl 2 (COD) x with Ph 2 PNMeNMePPh 2 and NaOMe in sec -butyl alcohol under argon at 85 °C affords the ruthenium dihydride Ru(Ph 2 PNMeNMePPh 2 ) 2 H 2 ( 1 ) in high yield. 1 reacts with CO, O 2, S 8, and CH 2 Cl 2, affording the complexes Ru(Ph 2 PNMeNMePPh 2 ) 2 (CO) ( 2 ), Ru(Ph 2 PNMeNMePPh 2 ) 2 (O 2 ) ( 3 ), Ru(Ph 2 PNMeNMePPh 2 ) 2 (S 2 ) ( 4 ), and Ru(Ph 2 PNMeNMePPh 2 ) 2 (H)(Cl) ( 5 ), respectively. 1 also reacts with PhC⋮CH, EtO 2 CC⋮CH, and C 6 H 6 by C−H activation, yielding the complexes Ru(Ph 2 PNMeNMePPh 2 ) 2 (H)(C⋮CPh) ( 6 ), Ru(Ph 2 PNMeNMePPh 2 ) 2 (H)(C⋮CCO 2 Et) ( 7 ), and Ru(Ph 2 PNMeNMePPh 2 ) 2 (H)(Ph) ( 8 ), respectively. The crystal structures of 3, 4 and 5 have been determined.