Ligand Effects in Calcium Catalyzed Ketone Hydroboration

The first naked (Lewis base-free) cationic Ca amidinate complex [(AmCa)-Am-tBu-Ca-DIPP(C6H6)](+)[B(C6F5)(4)](-) was prepared in 62 % yield {(AmDIPP)-Am-tBu = tBuC(N-DIPP)(2); DIPP = 2,6-diisopropylphenyl} by reaction of [(AmCaH)-Am-tBu-Ca-DIPP](2) with [Ph3C](+)[B(C6F5)(4)](-) in chlorobenzene. The ether-free complex (AmCaN)-Am-tBu-Ca-DIPP(SiMe3)(2) was obtained by removal of diethyl ether from its ether adduct. Crystal structures show that the amidinate ligand in both complexes is N,Aryl-chelating. In this coordination mode the bulk of the amidinate ligand is comparable to that of a DIPP-substituted beta-diketiminate ligand. Isomers with N,N-coordinating amidinate ligands are circa 15 kcal/mol higher in energy and this coordination mode is only present in case additional ether ligands compensate for energy loss or in case of space limitation at the metal, e.g. in homoleptic (Am-tBu(DIPP))(2)Ca. A series of four Ca amidinate complexes, (AmCaX)-Am-tBu-Ca-DIPP, were tested in the catalytic hydroboration of ketones and aldehydes by pinacolborane (HBpin). Catalytic activities increase for X- = I- < B(C6F5)(4)(-) < (Me3Si)(2)N- approximate to H-. For catalysts with unreactive anions, like I- or B(C6F5)(4)(-), catalyst performance increases with the Lewis acidity of the metal and a mechanism is proposed in which HBpin and ketone coordinate to the Ca2+ ion which is followed by direct hydroboration. The more active catalysts with X- = (Me3Si)(2)N- or H- likely operate through a mechanism which involves intermediate metal hydride (or borate) complexes.