Oxidative Addition of Allylic Substrates to Coordinatively Unsaturated Ruthenium Compounds, [Ru(<i>η</i><sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)(<i>η</i>-amidinate)]: Preparation, Structure Elucidation, and Catalysis of Novel Ruthenium (IV)-<i>η</i><sup>3</sup>-Allyl Complexes
作者:Hideo Kondo、Akira Kageyama、Yoshitaka Yamaguchi、Masa-aki Haga、Karl Kirchner、Hideo Nagashima
DOI:10.1246/bcsj.74.1927
日期:2001.10
coordinative unsaturation, gave novel cationic π-allyl ruthenium(IV) species. The compounds [Ru(η3-allyl)(η5-C5Me5)(η2-amidinate)]+X− were isolated by anion exchange of the products (X = PF6, BF4, BPh4), and were characterized by spectroscopic analysis. The crystallography of two of the [Ru(η3-allyl)(η5-C5Me5)(η2-amidinate)]+X− revealed a four-legged piano stool structure in which two nitrogen atoms in
烯丙基卤化物、乙酸盐和碳酸盐与 [Ru(η5-C5Me5)(η-脒)] [脒:iPrNC(Me)=NiPr (1a), tBuNC(Ph)=NtBu (1b)] 的氧化加成反应,其中显示出配位不饱和的迹象,产生了新的阳离子 π-烯丙基钌 (IV) 物种。化合物[Ru(η3-烯丙基)(η5-C5Me5)(η2-脒)]+X-通过产物(X = PF6、BF4、BPh4)的阴离子交换分离,并通过光谱分析表征。[Ru(η3-allyl)(η5-C5Me5)(η2-amidinate)]+X− 中两个的晶体学揭示了四足钢琴凳结构,其中脒配体中的两个氮原子和脒配体中的两个碳原子。 η3-烯丙基配体占据四条腿的位置;η3-烯丙基配体的取向是内向的。尽管前体[Ru(η5-C5Me5)(η-脒)]的循环伏安图,表明除烯丙基卤化物之外的有机卤化物可能氧化加成到[Ru(η5-C5Me5)(η-脒)],只有烯丙基卤