二氧化硫插入钯-氧键的反应：钯（II）的烷基亚硫酸酯配合物的制备

Insertion reactions of SO2 into Pd-OR bonds: preparation of alkyl sulfito complexes of palladium(II).

作者信息

Ruiz José, Martínez M Teresa, Florenciano Félix, Rodríguez Venancio, López Gregorio, Pérez José, Chaloner Penny A, Hitchcock Peter B

机构信息

Departamento de Química Inorgánica, Facultad de Quimica, Universidad de Murcia, 30071 Murcia, Spain.

出版信息

Dalton Trans. 2004 Mar 21(6):929-32. doi: 10.1039/b316697j. Epub 2004 Feb 10.

DOI:10.1039/b316697j

PMID:15252480

Abstract

Mononuclear palladium-hydroxo complexes of the type [Pd(N-N)(C6F5)(OH)][(N-N = 2,2'-bipyridine (bipy), 4,4'-dimethyl-2,2'-bipyridine (Me2bipy), or N,N,N',N'-tetramethylethylenediamine (tmeda) react with SO2(1 atm) at room temperature in alcohol (methanol, ethanol, propanol or isopropanol) to yield alkyl sulfito palladium complexes [Pd(N-N)(C6F5)(SO2OR)](R = Me, Et, Pr or iPr). Similar alkyl sulfito complexes [Pd(N-N)(C6F5)(SO2OR)](N-N = bis(3,5-dimethylpyrazol-1-yl)methane); R = Me or Et) are obtained when [Pd(N-N)(C6F5)Cl] is treated with KOH in the corresponding alcohol ROH and SO2 is bubbled through the solution. The reaction of [Pd(bipy)(C6F5)(OH)] with SO2 in tetrahydrofuran gives [Pd(N-N)(C6F5)(SO2OH)]. The X-ray diffraction study of [Pd(tmeda)(C6F5)(SO2OPr)] has established the sulfur coordination of the propyl sulfito ligand.

摘要

[Pd(N-N)(C6F5)(OH)]类型的单核钯-羟基配合物（其中N-N = 2,2'-联吡啶（bipy）、4,4'-二甲基-2,2'-联吡啶（Me2bipy）或N,N,N',N'-四甲基乙二胺（tmeda））在室温下于醇类（甲醇、乙醇、丙醇或异丙醇）中与SO2（1个大气压）反应，生成烷基亚硫酸钯配合物[Pd(N-N)(C6F5)(SO2OR)]（R = 甲基、乙基、丙基或异丙基）。当[Pd(N-N)(C6F5)Cl]在相应的醇ROH中用KOH处理并向溶液中通入SO2时，可得到类似的烷基亚硫酸配合物[Pd(N-N)(C6F5)(SO2OR)]（N-N = 双(3,5-二甲基吡唑-1-基)甲烷；R = 甲基或乙基）。[Pd(bipy)(C6F5)(OH)]在四氢呋喃中与SO2反应生成[Pd(N-N)(C6F5)(SO2OH)]。[Pd(tmeda)(C6F5)(SO2OPr)]的X射线衍射研究确定了丙基亚硫酸配体的硫配位情况。