P–H and P–P bond activation by Ni(I) and Fe(I) β-diketiminato-complexes

Reactions of ((NacNac)Ni)2(µ-η3-η3-C6H5Me) (NacNac = HC(CMeNC6H3(i-Pr)2)2) with PH2Ph or PHPh2 proceeds in a facile manner to afford the Ni(I)–phosphine adducts (NacNac)Ni(PH2Ph) 1 and (NacNac)Ni(PHPh2) 2, respectively. The related reactions of the Fe(I) complex (NacNac)Fe(η2-CH2CPh2) 3 with PH2Ph resulted in the formation of [(NacNac)Fe(µ2-PPh)]24. Alternatively 4 was also obtained from the reaction of [(NacNac)Fe(µ-Cl)]2 with PHPh2 and Na/K. The Ni(II) di-phosphosphine bridged compound [((NacNac)Ni)2(µ4-(PPh)2)] 5 was prepared via reaction of ((NacNac)Ni)2(µ-η3-η3-C6H5Me) with P5Ph5. Crystallographic data are reported for compounds 1–5.