Coordination modes of 2-mercaptonicotinic acid: synthesis and crystal structures of palladium(<scp>ii</scp>), platinum(<scp>ii</scp>), rhenium(<scp>iii</scp>) and molybdenum(<scp>vi</scp>) complexes
作者:Susana M. O. Quintal、Helena I. S. Nogueira、Vitor Félix、Michael G. B. Drew
DOI:10.1039/b206101e
日期:——
New Pd(II), Pt(II), Re(III), Mo (VI) and Mo(V) complexes with 2-mercaptonicotinic acid (HnicSH), [Pd(PPh3)(HnicS)2]·0.5CH3OH 1, [Pd(HnicS)2]·CH3OH 2, [Pt(PPh3)(HnicS)2]·NEt3·H2O 3, [Pt(HnicS)2]
4, [Pt(bipy)(HnicS)2]·CH3OH 5, [Re(PPh3)(OCH3)(HnicS)2]
6, [ReI2(PPh3)2(HnicS)]
7, [MoO2(CH3NicS)2]
8 and [Mo2O3(CH3nicS)4]·DMF 9 have been prepared. The crystal structures of compounds 1, 3, 8 and [ReI2(PPh3)2(HnicS)]·0.5H2O·DMF (7·0.5H2O·DMF) were determined by X-ray diffraction. Complexes 1 and 3 contain two HnicS− ligands bonded in two different coordination modes: monodentate (S) and chelating (N,S). Complexes 7 and 8 contain only one HnicS− ligand which is bidentate (N,S). Infrared, 1H and 13C-1H} NMR spectroscopic data for the complexes are presented. The Mo(VI) complex 8 is active towards oxygen atom transfer reactions and can catalyse the oxidation of benzoin and PPh3 with dmso; the catalysis occurs via the Mo(V) complex 9 which has been isolated and characterized.
新的Pd(II), Pt(II), Re(III), Mo(VI) 及 Mo(V) 配合物与2-巯基烟酸 (HnicSH) [Pd(PPh3)(HnicS)2]·0.5CH3OH 1, [Pd(HnicS)2]·CH3OH 2, [Pt(PPh3)(HnicS)2]·NEt3·H2O 3, [Pt(HnicS)2] 4, [Pt(bipy)(HnicS)2]·CH3OH 5, [Re(PPh3)(OCH3)(HnicS)2] 6, [ReI2(PPh3)2(HnicS)] 7, [MoO2(CH3NicS)2] 8 及 [Mo2O3(CH3nicS)4]·DMF 9 已经制备。化合物1,3,8 及 [ReI2(PPh3)2(HnicS)]·0.5H2O·DMF (7·0.5H2O·DMF) 的晶体结构已经用X射线衍射法测定。配合物1及3包含两个HnicS-配体与中心原子以两种不同的配位方式键合:单齿 (S) 和螯合 (N,S)。配合物7及8包含仅一个HnicS-配体以双齿 (N,S) 形式键接。配合物的红外,1H 及 13C-1H} NMR波谱数据也已经显示。Mo(VI) 配合物8具有转移氧原子的活性并可以催化苯偶姻及PPh3与dmso的氧化;催化反应是通过Mo(V) 配合物9进行的,而9已经被分离和得到表征。