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Factors affecting the coordination mode of an amidato group on aluminum will be presented. The reaction of N-tert-butylalkylacetamide ((t)BuNHCR([double bond]O)) with 1.1 molar equiv of Me(3)Al in refluxing hexane affords a pentacoordinated, dimeric compound [Me(2)Al[eta(2)-(t)BuNC(R)(mu(2)-O)]](2) (3, R = p-(t)Bu-C(6)H(4); 4, R = 2,6-F,F-C(6)H(3); 5, R = Me; 6, R = CF(3); 7, R = p-F(3)C-C(6)H(4)). However, in the presence of 2.2 molar equiv of Me(3)Al, N-tert-butyl-4-tert-butylbenzamide ((t)BuNHC(p-(t)Bu-C(6)H(4))([double bond]O in refluxing hexane gives [Me(2)Al[eta(2)-(t)BuNC(p-(t)Bu-C(6)H(4))(mu(2)-O)]AlMe(3)], 8. In contrast, the reaction of R'NHCR' '([double bond]O) with 1 molar equiv of R(3)Al at room temperature produces tetracoordinated, dimeric, eight-membered ring aluminum compounds [R(2)Al[mu,eta(2)-R'NC(R' ')O]](2) (9, R = Me, R' = 2,6-(i)Pr, (i)()Pr-C(6)H(3), R' ' = Ph; 10, R = Me, R' = (i)Bu, R' ' = Ph; 11, R = Et, R' = Bn, R' ' = Ph; 12, R = Me, R' = Ph, R' ' = CF(3); 13, R = Me, R' = Bn, R' ' = CF(3)). On the other hand, 4'-chlorobenzanilide ((p-Cl-C(6)H(4))NHCPh([double bond]O)) reacts with R(3)Al to produce trimeric, twelve-membered ring aluminum compounds [R(2)Al[mu, eta(2)-(p-Cl-C(6)H(4))NC(Ph)O]](3) (14, R = Me; 15, R = Et). Furthermore, the reaction of 2'-methoxybenzanilide with 1 molar equiv of Me(3)Al in hexane yields a dinuclear aluminum complex [Me(2)Al(o-OMe-Ph)NC(Ph)(O)AlMe(3)], 16.

No abstract

Polyesters containing thiolate chain end were obtained from the "controlled" ring-opening polymerization (ROP) of -caprolactone or δ-valerolactone initiated by several novel aluminum thiolates. The initiators, [(MOBT) 2AlR] (1, R ) Me; 2, R ) Cl) can be obtained in high yield from the interaction of Me3Al or Et2AlCl with 2 molar equiv of 2-methoxybenzenethiol (MOBT-H). [(µ-TMBM)AlR2]2 (3, R ) Et; 4, R ) Me; 5, R ) Bu i ) were prepared from the reactions of R3Al with 1 molar equiv of 2,4,6-trimethylbenzylmercaptan (TMBM-H) in dichloromethane at ambient temperature. The X-ray structures of 1-3 have been determined and have shown that 1 and 2 are monomeric while 3 is dimeric in the solid state. The "controlled" character of the aluminum complex shown in the polymerization process has enabled us to synthesize a P-δ-VL-b-P--CL block copolymer, and the thioester end group may provide a suitable method for the design of PCL conjugates. In addition, ROP of L-lactide initiated by 1 can be achieved under refluxing toluene conditions.

A series of degradable block copolymers, poly(acrylonitrile)-b-poly( -caprolactone) (PAN-PCL), have been synthesized by sequential living polymerization in this study. Well-defined, microphase-separated PAN-PCL microdomains can be efficiently achieved in the bulk by using appropriate solvents. The microphase-separated lamellar samples were then used as templates to produce mesoporous carbons at which large amounts of porous texture in carbonized PAN matrix were formed after degradation of PCL due to randomly oriented lamellar texture (namely, interconnection of PCL microdomains). The thermal profiles for efficient stabilization were examined by differential scanning calorimetry and thermogravimetric analyses as well as Fourier transform infrared spectroscopy. Consequently, mesoporous carbon materials might be prepared as evidenced by transmission electron microscopy, field emission scanning electron microscopy, and small-angle X-ray scattering. The formation of carbonized materials was identified in accordance with the presence of carbon diffractions by wide-angle X-ray diffraction. In contrast to the thermal stability of the carbonization of PAN homopolymers, it is noted that the carbonization procedure can be achieved in the PAN-PCL system regardless of the stretching process (that is an essential process to improve the thermal stability of PAN carbonization). We speculate that this unique feature for the carbonization of PAN copolymers might be attributed to the stretched chains of PAN under nanoscale confined environment.