| 17940652 |
Tanabe Y, Kajitani H, Iwasaki M, Ishii Y: Synthesis and reactivities of a bis (cyanamido)-capped triruthenium complex. Dalton Trans. 2007 Nov 7;(41):4701-7. Epub 2007 Aug 22.
The tetraruthenium complex [Cp*RuCl] 4 (Cp* = eta (5)-C (5) Me (5)) reacts with Na (2) NCN to afford the anionic bis (cyanamido)-capped triruthenium complex [(Cp*Ru) 3 (micro (3)-NCN)(2)]- ((2-)), which undergoes single electron oxidation to form [(Cp*Ru) 3 (micro (3)-NCN) 2] upon workup with 1 equiv. of [Cp (2) Fe](PF (6)) (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 [(Cp*Ru) 3 (micro-H)(micro-NCN) 2], while the cationic side-on NCNH (2) complex [(Cp*Ru) 3 (micro-Cl)(micro (3)-NCN)(micro (3)-NCNH (2)-1kappaC,N:2kappaC:3kapp aN)] 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)[(Cp*Ru)(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)[(Cp*Ru) 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 [(Cp*Ru) 3 (micro (3)-NCN){(micro (4)-NCN)(AuPPh (3))}] (8) or the benzoylcyanamido complex [(Cp*Ru) 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. |
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