ALUMINUM COMPLEXES INCORPORATING BULKY NITROGEN AND SULFUR DONOR LIGANDS

The synthesis and structures of aluminum complexes incorporating bulky thioamidate (RC(NR')S-), thioureido (R'HNC(NR')S-), and amidinate (RC (NR')(2)(-)) ligands are described. The reaction of AlMe3 with AdN=C=S (Ad = 1-adamantyl) affords the insertion product {MeC(NAd)S}AlMe2 (1) , which binds 1 equiv of AlMe3 to generate {MeC(NAd)S}AlMe2. AlMe3 (2) . The alkane elimination reaction of AlMe3 and N,N'-disubstituted thio urea derivatives, (R'HN)(2)C=S, affords thioureido complexes {R'HNC(NR ')S}AlMe2 (3a, R' = Ad; 3b, R' = Ar = 2,6-Pr-i(2)-Ph). Carbodiimides, R'N=C=NR', react with AlMe3 to afford acetamidinate compounds {MeC(NR' )(2)}AlMe2 (4a, R' = Ad; 4b, R' = Ar). Sequential addition of (BuLi)-B u-t and AlX2Cl (X = Cl, Me) to R'N=C=NR' affords pivamidinate compound s {(BuC)-Bu-t(NR')(2)}AlCl2 (5b, R' = Ar) and {(BuC)-Bu-t(NR')(2)}AlMe 2 (6a, R' = Ad; 6b, R' = Ar). Complexes 1, 3a, 6a, and 6b have been ch aracterized by X-ray crystallography.