demonstrating that the binding of two additional methyl carbanions compensates for the effect of the higher metal oxidation state. While the organoplatinum(II) species are emissive, the tetramethylplatinum(IV) complexes are photoreactive and undergo metal-to-ligand methyl transfer reactionsin agreement with the structurally confirmed weaker bonding to the axial methyl groups.
1,4-二取代的1,4-二氮杂
1,3-丁二烯螯合
配体RN CHCH NR(R-
DAB; R =烷基,芳基)与有机
铂片段PtMe 2,PtMe 4和PtMes 2(Mes = mesityl)已经准备好并就其电子结构进行了表征。所有化合物的特征都在于,低能电荷转移跃迁到R-
DAB
配体的低位π*轨道,无论是
金属d轨道(Pt II)还是
金属-碳σ键组合(Pt IV)。通过对HN CHCH NH与PtMe 2或PtMe 4之间的模型复合体进行DFT计算,可以支持这些光谱分配。该计算还重现了CyN CHCH NCy和PtMe 4之间的复合物的结构结果,该复合物显示出与轴向甲基基团明显更长的Pt-C键。描述了长波长跃迁的独特溶剂变色现象,以及可逆还原为Pt IV(R-
DAB • -)或Pt II(R-
DAB • -)物种的UV / vis光谱电
化学结果(无Pt证据)我声明)。相比之下,除了二聚三
氨合
铂