80659-24-1Relevant academic research and scientific papers
Some ruthenium complexes containing cyanocarbon ligands: Syntheses, structures and extent of electronic communication in binuclear systems
Bruce, Michael I.,Buntine, Mark A.,Costuas, Karine,Ellis, Benjamin G.,Halet, Jean-Fran?ois,Low, Paul J.,Skelton, Brian W.,White, Allan H.
, p. 3308 - 3326 (2007/10/03)
The preparation of several ruthenium complexes containing cyanocarbon anions is reported. Deprotonation (KOBu′) of [Ru(NCCH2Ph3)2Cp]PF6 (1) gives Ru{N=C=CH(CN)}(PPh3)2Cp (2), which adds a second [Ru(PPh3)2Cp]+ unit to give [{Ru(PPh3)2Cp}2 (μ-NCCHCN)]+ (3). Attempted deprotonation of the latter to give the μ-NCCCN complex was unsuccessful. Similar chemistry with tricyanomethanide anion gives Ru{N=C=C(CN)2} (PPh3)2Cp (4) and [{Ru(PPh3) 2Cp} 2 {μ-NCC(CN)CN}]PF6(5), and with pentacyanopropenide, Ru{N=C=C(CN)C(CN)C(CN)2} (PPh3)2Cp (6) and [{Ru(PPh3)2Cp}2 {μ-NCC(CN)C(CN)C(CN)CN}]PF6 (7). The Ru(dppe)Cp* analogues of 6 and 7 (8 and 9) were also prepared. Thermolysis of 6 (refluxing toluene, 12 h) results in loss of PPh3 and formation of the binuclear cyclic complex {Ru(PPh3) Cp[μ-N=C={C(CN)=C(CN)2}CN]}2 (10). The solid-state structures of 2-4 and 8-10 have been determined and the nature of the isomers shown to be present in solutions of the binuclear cations 7 and 9 by NMR studies has been probed using Hartree-Fock and density functional theory.
Syntheses, structures, and electronic interactions of dicyanamide/tricyanomethanide-bridged binuclear organometallic complexes
Zhang, Li-Yi,Shi, Lin-Xi,Chen, Zhong-Ning
, p. 633 - 640 (2008/10/08)
Dicyanamide-bound mononuclear compounds Cp(dppe)FeN(CN)2 (3) and Cp(PPh3)2RuN(CN)2 (4) were isolated in high yields by the reactions of Cp(dppe)FeCl (1) and Cp(PPh3)2RuCl (2), respectively, with excess sodium dicyanamide. Compounds 3 and 4 are excellent precursors for the design of dicyanamide-bridged binuclear complexes [{Cp(dppe)Fe}2N(CN)2](SbF6) (5) and [{Cp(PPh3)2Ru}2N(CN)2] (SbF6) (6) by the incorporation with 1 and 2, respectively. Controlling oxidation of 5 with ferrocenium hexafluorophosphate afforded the mixed-valence compound [{Cp(dppe)Fe}2N(CN)2](PF6)2 (5a) which exhibits a broad absorption band in the near-infrared region (centered at 1500 nm, ε = 750 cm-1 M-1) due to the intervalence charge transfer of Robin and Day class II mixed-valence system. Tricyanomethanide-bound mononuclear compounds Cp(dppe)FeC(CN)3 (7) and Cp(PPh3)2RuC(CN)3 (8) were prepared by the same methods as 3 and 4 using potassium tricyanomethanide as the starting material instead. The tricyanomethanide-bridged binuclear complexes [{Cp(dppe)Fe}2C(CN)3](CF3SO3) (9) and [{Cp(PPh3)2- Ru}2C(CN)3](SbF6) (10) were prepared by the reactions between 7 and 1 and between 8 and 2, respectively. Cyclic voltammograms of the dicyanamide/tricyanomethanide-bridged binuclear complexes showed stepwise reversible one-electron oxidation waves with the potential separation of the two redox couples in the range 0.14-0.25 V, indicating the demonstrably electronic communication is operative between the organometallic components through a dicyanamide/tricyanomethanide spacer with metal...metal distances more than 7.8 A. Furthermore, the electronic coupling transmitted by the tricyanomethanide is appreciably greater than that by the dicyanamide. The complexes 3-10 were characterized by elemental analysis, IR, UV-vis, 1H and 31P NMR, and ES-MS. The crystal structures of 3 and 5-9 were determined by X-ray crystallography.
