School of Chemistry, University of New South Wales, NSW 2052, Australia.
Inorg Chem. 2012 Mar 19;51(6):3733-42. doi: 10.1021/ic2027225. Epub 2012 Mar 6.
Treatment of trans-[FeCl(2)(dmpe)(2)] with phenylhydrazine and 1 equiv of base afforded the side-on bound phenylhydrazido complex cis-Fe(η(2)-NH(2)NPh)(dmpe)(2). Further deprotonation of the phenylhydrazido complex afforded the side-on bound phenyldiazene complex cis-[Fe(η(2)-HN═NPh)(dmpe)(2)] as a mixture of diastereomers. Treatment of cis-[RuCl(2)(dmpe)(2)] with phenylhydrazine or methylhydrazine afforded the end-on bound phenylhydrazine or methylhydrazine complexes cis-RuCl(η(1)-NH(2)NHR)(dmpe)(2) (R = Ph, Me). Treatment of the substituted hydrazine complexes with base afforded the side-on bound phenylhydrazido complex cis-Ru(η(2)-NH(2)NPh)(dmpe)(2) as well as the phenyldiazene and methyldiazene complexes cis-[Ru(η(2)-HN═NR)(dmpe)(2)] (R = Ph, Me). cis-RuCl(η(1)-NH(2)NHR)(dmpe)(2) (R = Ph, Me), cis-M(η(2)-NH(2)NPh)(dmpe)(2) (M = Fe, Ru) and cis-[Ru(η(2)-HN═NPh)(dmpe)(2)] were characterized structurally by X-ray crystallography. cis-[Ru(η(2)-HN═NPh)(dmpe)(2)] is the first side-on bound phenyldiazene complex to be structurally characterized. In the structure of cis-[Ru(η(2)-HN═NPh)(dmpe)(2)], the geometry of the coordinated diazene fragment is significantly nonplanar (CNNH angle 137°) suggesting that the complex is probably better described as a Ru(II) metallodiaziridine than a Ru(0) diazene π-complex.
用苯肼和 1 当量的碱处理[FeCl(2)(dmpe)(2)]，得到侧接绑定的苯腙配合物 cis-Fe(η(2)-NH(2)NPh)(dmpe)(2)。进一步对苯腙配合物进行去质子化，得到侧接绑定的苯亚氨基配合物 cis-[Fe(η(2)-HN═NPh)(dmpe)(2)]，其为非对映异构体混合物。用苯肼或甲肼处理 cis-[RuCl(2)(dmpe)(2)]，得到端接绑定的苯肼或甲肼配合物 cis-RuCl(η(1)-NH(2)NHR)(dmpe)(2)（R = Ph，Me）。用碱处理取代的肼配合物，得到侧接绑定的苯腙配合物 cis-Ru(η(2)-NH(2)NPh)(dmpe)(2)，以及苯亚氨基和甲亚氨基配合物 cis-[Ru(η(2)-HN═NR)(dmpe)(2)]（R = Ph，Me）。cis-RuCl(η(1)-NH(2)NHR)(dmpe)(2)（R = Ph，Me），cis-M(η(2)-NH(2)NPh)(dmpe)(2)（M = Fe，Ru）和 cis-[Ru(η(2)-HN═NPh)(dmpe)(2)]通过 X 射线晶体学进行了结构表征。cis-[Ru(η(2)-HN═NPh)(dmpe)(2)]是第一个通过结构特征确定的侧接绑定的苯亚氨基配合物。在 cis-[Ru(η(2)-HN═NPh)(dmpe)(2)]的结构中，配位的二氮烯片段的几何形状明显非平面（CNNH 角 137°），表明该配合物可能更适合描述为 Ru(II)金属二氮杂环丁烷，而不是 Ru(0)二氮烯π-配合物。
