Alkali metal complexes as efficient catalysts for hydroboration and cyanosilylation of carbonyl compounds.

We report here reactions between the N-adamantyliminopyrolyl ligand 2-(AdN[double bond, length as m-dash]CH)-C4H3NH (L-H) and alkali metal hexamethyldisilazides [MN(SiMe3)2] (M = Li, Na and K) to afford the dimeric [{2-(AdN[double bond, length as m-dash]CH)-C4H3NLi(THF)}2] (1), [{2-(AdN[double bond, length as m-dash]CH)-C4H3N}{Na(THF)1.5}2] (2) and polymeric [{2-(AdN[double bond, length as m-dash]CH)-C4H3NK(THF)}n] (3) complexes at ambient temperature. A one-pot reaction between L-H, [KN(SiMe3)2] and alkaline earth metal diiodide (AeI2) in a 2 : 2 : 1 molar ratio, which resulted in the formation of a heteroleptic Ae metal complex [κ2-{2-(AdN[double bond, length as m-dash]CH)-C4H3N}2Ae(THF)2] [Ae = Mg (4), Ca (5)], is also reported.

Ring Opening Polymerization and Copolymerization of Cyclic Esters Catalyzed by Group 2 Metal Complexes Supported by Functionalized P-N Ligands.

We report the preparation of alkali and alkaline earth (Ae) metal complexes supported by 2-picolylamino-diphenylphosphane chalcogenide [(PhP(=E)NHCH(CHN)] [E = S (1-H); Se (2-H)] ligands. The treatment of the protic ligand, 1-H or 2-H, with alkali metal hexamethyldisilazides at room temperature afforded the corresponding alkali metal salts [M(THF)(PhP(=E)NCH(CHN)] [M = Li, E = S (3a), Se (3b)] and [{M(THF) (PhP(=E)NCH(CHN)}] [M = Na, E = S (4a), Se (4b); M = K, E = Se (5b)] in good yield. The homoleptic Ae metal complexes [κ-(PhP(=Se)NCH(CHN)Mg(THF)] (6b) and [κ-{(PhP(=Se)NCH(CHN)}M(THF) ] (M = Ca (7b), Sr (8b), Ba (9b)] were synthesized by the one-pot reaction of 2-H with [KN(SiMe)] and MI in a 2:2:1 molar ratio at room temperature.