Well‐Defined Cationic Alkyl– and Alkoxide–Aluminum Complexes and Their Reactivity with ε‐Caprolactone and Lactides

Abstract

We describe the synthesis, structure, and reactivity of low-coordinate Al-alkyl and -alkoxide cationic complexes incorporating the sterically bulky aminophenolate bidentate ligand 6-(CH(2)NMe(2))-2-CPh(3)-4-Me-C(6)H(2)O- (N,O). These complexes are derived from the ionization of neutral dialkyl Al complexes (N,O)Al2) (1 a, R=Me; 1 b, R=iBu), readily obtained by alkane elimination between AlR3 and the corresponding aminophenol ligand, with the alkyl abstracting reagents B(C(6)F(5))3 and [Ph(3)C][B(C(6)F(5))4]. The reactions of 1 a,b with B(C(6)F(5))3 yield complicated mixtures or decomposition products, however the ionization of the Al-diisobutyl derivative 1 b with [Ph(3)C][B(C(6)F(5))4] affords a stable four-coordinate Al-PhBr cationic adduct [(N,O)Al(iBu)(PhBr)]+ (3+), as deduced from elemental analysis data. Complex 3+ readily coordinates Lewis bases such as THF to form the corresponding adduct [(N,O)Al(iBu)(thf)]+ (4+), and also rapidly chain-transfers with 1-hexene to yield the three-coordinate Al-hexyl cation [(N,O)Al-hexyl]+ (5+). Both cations 3+ and 5+ slowly dimerize to form unprecedented organoaluminum dications [(N,O)AlR+]2 (3'++, R=iBu; 5'++, R=hexyl) as deduced from X-ray crystallographic analysis. Cation 3+ reacts quickly with iPrOH to form a stable Lewis acid/base adduct [(N,O)Al(iBu)(HOiPr)]+ (6+), which constitutes the first X-ray characterized adduct between an Al-alkyl complex and a simple ROH. The Al-ROH proton in 6+ is readily abstracted by NMe(2)Ph to form the neutral isopropoxide Al complex [(N,O)Al(iBu)(OiPr)] (7). Upon reaction with THF, cation 6+ undergoes an intramolecular proton transfer to yield the ammonium Al-THF complex [(eta1-HN,O)Al(iBu)(OiPr)(thf)] (8 b+), in which the aminophenolate is eta1-coordinated to the Al center. Cation 8 b+ can then be converted to the desired Al-alkoxide derivative [(N,O)Al(OiPr)(thf)](+) (10+), by an intramolecular protonolysis reaction, as confirmed by X-ray crystallography. The synthesized Al-alkyl cations form robust four-coordinate adducts in the presence of cyclic esters such as epsilon-caprolactone and (D,L)-lactide, but no insertion chemistry occurs, illustrating the poor ability of the Al-R+ moiety to ring-open. In contrast, the Al-alkoxide cation 10+ polymerizes epsilon-caprolactone in a controlled manner with excellent activity, but is inactive in the polymerization of (D,L)-lactide and L-lactide. Control experiments with L-lactide show that cation 10+ ring-opens L-lactide to yield a robust five-coordinated Al--lactate cation [(N,O)Al(eta2-L-lactate-OiPr)(thf)]+ (13+), derived from a monoinsertion of L-lactide into the Al--OiPr bond of 10+, that does not further react. Cation 13+ may be regarded as a structurally characterized close mimic of the initial intermediate in the ring opening polymerization (ROP), of lactides by [{LX}M(OR)(L)] (where LX-=bidentate monoanionic ligand and L=labile ligand) metal complex initiators.