Addition of Amines to a Carbonyl Ligand: Syntheses, Characterization, and Reactivities of Iridium(III) Porphyrin Carbamoyl Complexes
作者:Taiwo O. Dairo、Arkady Ellern、Robert J. Angelici、L. Keith Woo
DOI:10.1021/om500189a
日期:2014.5.12
carbamoyl complexes (TTP)Ir(L)[C(O)NHR] (L = RNH2 (2a–d), 1-MeIm (4a), P(OEt)3 (5b), PMe2Ph (6c)) reacted with methyl iodide to give the iodo complexes (TTP)Ir(L)I (L = RNH2 (11a–d), 1-MeIm (12), P(OEt)3 (13), PMe2Ph (14)). Reactions of the complexes [(TTP)Ir(PMe2Ph)]BF4 (9) and [(TTP)IrP(OEt)3]BF4 (10) with [Bu4N]I, benzylamine (BnNH2), and PMe2Ph afforded (TTP)Ir(PMe2Ph)I (14), (TTP)Ir[P(OEt)3]I (13),
(羰基)氯的处理(内消旋-四-对- tolylporphyrinato)铱(III),(TTP)的Ir(CO)Cl(上1),具有在钠存在下,在23℃下过量的伯胺2 CO 3产生反胺配位的铱氨基甲酰基络合物(TTP)Ir(NH 2 R)[C(O)NHR](R = Bn(2a),n -Bu(2b),i -Pr(2c),t -Bu(2d)),分离产率高达94%。该反式-胺配体不稳定,可用奎宁环(1-氮杂双环[2.2.2]辛烷,ABCO),1-甲基咪唑(1-MeIm),亚磷酸三乙酯(P(OEt)3)和二甲基苯基膦(PMe 2 Ph代替))在23°C下得到六配位的氨基甲酰基络合物(TTP)Ir(L)[C(O)NHR](对于R = Bn:L = ABCO(3a),1-MeIm(4a),P(OEt)3(5a),PMe 2 Ph(6a))。上的配体置换反应和平衡的研究中,配体结合强度的金属铱中心为基准被发现的顺序PME降低2博士>