Backbone Reactivity of Manganese(I) NacNac Complexes

High Resolution Image Download MS PowerPoint Slide The reactivity of manganese(I) NacNac complexes was investigated toward various substrates for potential catalytic applications. The reaction of the five-coordinate β-diketiminate complex [Mn(La)(CO) 3 ] (La: MeC(NAr)CRC(NAr)Me, Ar = 2,6-Me 2 Ph, R = H 2a ) with formaldehyde allowed the isolation of complex [Mn(La–H 2 CO)(CO) 3 ] ( 3a ), where the aldehyde had added with the formation of a C–C and Mn–O bond. Similarly, reactions of the β-diketiminate complexes with acetylene and phenylacetylene resulted in [Mn(Lx–R′C 2 H)(CO) 3 ] (x = a Ar = 2,6-Me 2 Ph R′ = H, 4a, R′ = Ph 5a; x = b Ar = Ph, R′ Ph 4b ). In contrast, the β-diketiminate Mn(I) complex 2a reacted with the labile coordination of acetonitrile which could be removed via vacuum. However, nitrile insertion was observed with the β-diketimine complexes of the type [MnBr(CO) 3 (HLx)]. The nitrile moiety was inserted into the α–C-H bond of the LxH ligand via the formation of a C–C and Mn–N bond, giving [Mn(Lx–R″CNH)(CO) 3 ] (x = a Ar = 2,6-Me 2 Ph R″ = Me 6a, R″ = Ph 7a; x = c Ar = Ph, R″ = Me 6c ). This versatile reactivity of β-diketiminate and β-diketimine manganese(I) complexes delivers important knowledge for future investigations of their catalytic properties.