Tanabe Yoshiaki, Kajitani Hidenobu, Iwasaki Masakazu, Ishii Youichi
Department of Applied Chemistry, Faculty of Science and Engineering, Chuo University, Kasuga, Tokyo 112-8551, Japan.
Dalton Trans. 2007 Nov 7(41):4701-7. doi: 10.1039/b708328a. Epub 2007 Aug 22.
The tetraruthenium complex [CpRuCl]4 (Cp = eta(5)-C(5)Me(5)) reacts with Na(2)NCN to afford the anionic bis(cyanamido)-capped triruthenium complex [(CpRu)3(micro(3)-NCN)(2)]- ((2-)), which undergoes single electron oxidation to form [(CpRu)3(micro(3)-NCN)2] upon workup with 1 equiv. of Cp(2)Fe (Cp = eta(5)-C(5)H(5)). Treatment of (2-) with 1 equiv. of HCl at room temperature leads to the protonation of one of the Ru-Ru edges to give the hydrido-bridged complex [(CpRu)3(micro-H)(micro-NCN)2], while the cationic side-on NCNH(2) complex [(CpRu)3(micro-Cl)(micro(3)-NCN)(micro(3)-NCNH(2)-1kappaC,N:2kappaC:3kappaN)]Cl (5) is obtained by the reaction of (2-) with an excess amount of HCl at -78 degrees C. On the other hand, the reaction of (2-) with BR(3) (R = Et, Ph) results in the ligation of two BR(3) molecules to the terminal nitrogen atoms of the cyanamido ligands to yield the bis(borane) adduct (PPN)[(CpRu)(3){(micro(4)-NCN)(BR(3))}(2)] (6, PPN = Ph(3)PNPPPh(3)). 6b (R = Et) slowly liberates one BEt(3) molecule in acetone to give the mono(borane) adduct (PPN)[(CpRu)3(micro(3)-NCN){(micro(4)-NCN)(BEt(3))}] (7). (2-) is also shown to react with [AuCl(PPh(3))] or PhCOCl to afford the tetranuclear heterometallic complex [(CpRu)3(micro(3)-NCN){(micro(4)-NCN)(AuPPh(3))}] (8) or the benzoylcyanamido complex [(CpRu)3(micro(3)-NCN)(micro(3)-NCNCOPh)] in which the Au(PPh(3))+ or benzoyl fragment is bound to the terminal nitrogen atom of a cyanamido ligand. The molecular structures of PPN+(2-), 5.C(6)H(6), 7 and 8.C(6)H(6) have been determined by single-crystal X-ray analyses.
四钌配合物[CpRuCl]₄（Cp = η⁵-C₅Me₅）与Na₂NCN反应，得到阴离子型双（氰胺基）封端的三钌配合物[(CpRu)₃(μ₃-NCN)₂]⁻（(2⁻)），经单电子氧化后，用1当量的Cp₂Fe（Cp = η⁵-C₅H₅）后处理得到[(CpRu)₃(μ₃-NCN)₂]。室温下用1当量的HCl处理(2⁻)，会使其中一条Ru-Ru边质子化，得到氢桥联配合物[(CpRu)₃(μ-H)(μ-NCN)₂]，而阳离子型侧基NCNH₂配合物[(CpRu)₃(μ-Cl)(μ₃-NCN)(μ₃-NCNH₂-1κC,N:2κC:3κN)]Cl（5）是通过(2⁻)与过量HCl在-78℃反应得到的。另一方面，(2⁻)与BR₃（R = Et，Ph）反应，会使两个BR₃分子与氰胺基配体的末端氮原子配位，生成双（硼烷）加合物(PPN)[(CpRu)₃{(μ₄-NCN)(BR₃)}₂]（6，PPN = Ph₃PNPPPh₃）。6b（R = Et）在丙酮中会缓慢释放出一个BEt₃分子，得到单（硼烷）加合物(PPN)[(CpRu)₃(μ₃-NCN){(μ₄-NCN)(BEt₃)}]（7）。还表明(2⁻)与[AuCl(PPh₃)]或PhCOCl反应，分别得到四核异金属配合物[(CpRu)₃(μ₃-NCN){(μ₄-NCN)(AuPPh₃)}]（8）或苯甲酰氰胺基配合物[(CpRu)₃(μ₃-NCN)(μ₃-NCNCOPh)]，其中Au(PPh₃)⁺或苯甲酰片段与氰胺基配体的末端氮原子相连。通过单晶X射线分析确定了PPN⁺(2⁻)、5·C₆H₆、7和8·C₆H₆的分子结构。
