The co-ordination of small molecules by manganese(II) phosphine complexes. Part 11. The co-ordination of dioxygen by manganese(II) complexes containing long-chain phosphine ligands
作者:David S. Barratt、George A. Gott、Charles A. McAuliffe
DOI:10.1039/dt9880002065
日期:——
Manganese(II) complexes of long-chain phosphines, [MnX2(phosphine)][X = Cl, Br, or I; phosphine = P(C12H25)3, P(C14H29)3, P(C16H33)3, PPh(C12H25)2, PPh(C14H29)2, or PPh(C16H33)2], have been prepared. They form highly coloured 1 : 1 adducts with dioxygen, [MnX2(phosphine)(O2)], in both toluene and tetrahydrofuran (thf) solution. Infrared and e.s.r. spectra strongly suggest that these [MnX2(phosphine)]
锰(II长链膦,[MNX的)配合物2(膦)] [X =氯,溴,或I; 膦= P(C 12 H 25)3,P(C 14 H 29)3,P(C 16 H 33)3,PPh(C 12 H 25)2,PPh(C 14 H 29)2或PPh(制备了C 16 H 33)2 ]。它们与双氧形成[MnX 2(膦)(O 2)],同时在甲苯和四氢呋喃(thf)溶液中使用。红外光谱和esr光谱强烈表明,这些[MnX 2(膦)]络合物是固态和甲苯中的拟四面体二聚体,与先前报道的[Mnl 2(PPhMe 2)]结构形成鲜明对比。一些分子量数据表明在甲苯中的双加氧产物是单体的[MnX 2(膦)(O 2)]种类。获得了甲苯和thf溶液的双氧结合曲线,并推导出了双氧反应的平衡常数K O 1。一般观察到K O 2增加,并且P 50是50%的位点被脱氧时的分压,随着两种溶剂中卤化物配体从Cl到Br到I的变化而降低,这反映了早