"Cl\u00E9ment, S." . . "20" . "7"^^ . . "RIV/61388955:_____/11:00369086!RIV12-AV0-61388955" . . "Edge, R." . . "electrochemistry; vinyl complexes; ruthenium"@en . "Z\u00E1li\u0161, Stanislav" . "Winter, R. F." . . "1"^^ . . "0022-328X" . "Electron delocalization in vinyl ruthenium substituted cyclophanes: Assessment of the through-space and the through-bond pathways"@en . . "696" . . "Collison, D." . "Journal of Organometallic Chemistry" . "[15455555C314]" . "000293999500010" . . . . . . "Electron delocalization in vinyl ruthenium substituted cyclophanes: Assessment of the through-space and the through-bond pathways" . "10.1016/j.jorganchem.2011.06.028" . "M\u00FCcke, P." . . . "Pseudo-para[2.2]paracyclophane- and [2.1]orthocyclophane-bridged diruthenium complexes 2 and 3 with two interlinked electroactive styryl ruthenium moieties have been prepared and investigated. Both complexes undergo two reversible consecutive one-electron oxidation processes which are separated by 270 or 105 mV. Stepwise electrolysis of the neutral complexes to first the mixed-valent radical cations and then the dioxidized dications under IR monitoring reveal incremental shifts of the charge-sensitive Ru(CO) bands and allow for an assignment of their radical cations as moderately or very weakly coupled mixed-valent systems of class II according to Robin and Day. Ground-state delocalization in the mixed-valent forms of these complexes as based on the CO band shifts is considerably larger for the %22closed%22 paracyclophane as for the %22half-open%22 orthocyclophane. Experimental findings are backed by the calculated IR band patterns and spin density distributions for radical cations of slightly simplified model complexes 2Me(.+) and 3Me(.+) with the P(i)Pr(3) ligands replaced by PMe(3). Radical cations 2(.+) and 3(.+) feature a characteristic NIR band that is neither present in their neutral or fully oxidized forms nor in the radical cation of the monoruthenium [2.2] paracyclophane complex 1 with just one vinyl ruthenium moiety. These bands are thus assigned as intervalence charge-transfer (IVCT) transitions. Our results indicate that, for the radical cations, electronic coupling %22through-space%22 via the stacked styrene decks is significantly more efficient than the %22through-bond%22 pathway."@en . . . "197094" . "CH - \u0160v\u00FDcarsk\u00E1 konfederace" . "12"^^ . "Electron delocalization in vinyl ruthenium substituted cyclophanes: Assessment of the through-space and the through-bond pathways"@en . "RIV/61388955:_____/11:00369086" . "Zabel, M." . "Pseudo-para[2.2]paracyclophane- and [2.1]orthocyclophane-bridged diruthenium complexes 2 and 3 with two interlinked electroactive styryl ruthenium moieties have been prepared and investigated. Both complexes undergo two reversible consecutive one-electron oxidation processes which are separated by 270 or 105 mV. Stepwise electrolysis of the neutral complexes to first the mixed-valent radical cations and then the dioxidized dications under IR monitoring reveal incremental shifts of the charge-sensitive Ru(CO) bands and allow for an assignment of their radical cations as moderately or very weakly coupled mixed-valent systems of class II according to Robin and Day. Ground-state delocalization in the mixed-valent forms of these complexes as based on the CO band shifts is considerably larger for the %22closed%22 paracyclophane as for the %22half-open%22 orthocyclophane. Experimental findings are backed by the calculated IR band patterns and spin density distributions for radical cations of slightly simplified model complexes 2Me(.+) and 3Me(.+) with the P(i)Pr(3) ligands replaced by PMe(3). Radical cations 2(.+) and 3(.+) feature a characteristic NIR band that is neither present in their neutral or fully oxidized forms nor in the radical cation of the monoruthenium [2.2] paracyclophane complex 1 with just one vinyl ruthenium moiety. These bands are thus assigned as intervalence charge-transfer (IVCT) transitions. Our results indicate that, for the radical cations, electronic coupling %22through-space%22 via the stacked styrene decks is significantly more efficient than the %22through-bond%22 pathway." . . "Electron delocalization in vinyl ruthenium substituted cyclophanes: Assessment of the through-space and the through-bond pathways" . . "P(KAN100400702), P(LD11086), Z(AV0Z40400503)" .