Synthesis and Structure of Neutral and Cationic Aluminum Complexes Supported by Bidentate <i>O</i>,<i>P</i>-Phosphinophenolate Ligands and Their Reactivity with Propylene Oxide and ε-Caprolactone
作者:Mansour Haddad、Mohamed Laghzaoui、Richard Welter、Samuel Dagorne
DOI:10.1021/om9003362
日期:2009.8.10
The O,P-type phosphinophenol ligands 1a−c were found to readily react with 1 equiv of AlMe3 to afford in high yields the corresponding Al chelate complexes η2-O,P-(2-PPh2-4-R′-6-R-C6H2O)}AlMe2, 2a−c (R = Me, R′ = H, 2a; R = Ph, R′ = H, 2b; R = tBu, R′ = Me, 2c). The bis-adduct Al methyl complexes η2-O,P-(2-PPh2-4-R′-6-R-C6H2O)}2AlMe (R = Ph, R′ = H, 3b; R = tBu, R′ = Me, 3c) also formed quantitatively
发现O,P型膦基苯酚配体1a - c容易与1当量的AlMe 3反应,以高收率提供相应的Al螯合物[ 2 -O,P-(2-PPh 2 -4-R' -6-RC 6 H ^ 2 O)}阿尔梅2,图2a - ç(R = Me中,R'= H,2a中; R =苯基,R'= H,2b中; R =吨卜,R'= Me中,图2c)。的双加合物的Al甲基络合物η 2 -O,P-(2-PPH 2 -4-R'-6-RC 6 H ^ 2 O)} 2AlMe(R = Ph,R'= H,3b ; R = t Bu,R'= Me,3c)在膦基酚1b,c与0.5当量的AlMe 3反应时也定量形成。单加成和双加成Al甲基物质2a - c和3b,c都是稳定的单体形式,无论是在溶液中还是在固态,并且在配位溶剂如thf中均保持稳定。与此相反,双-加合物的Al甲基络合物3c中经历在醇源的存在下进行配位体交换反应(我异丙醇,BnOH)以产生均配型三-加合物的Al复合η