%0 Journal Article %1 Naklicki.2012 %A Naklicki, Mark L. %A Gorelsky, Serge I. %A Kaim, Wolfgang %A Sarkar, Biprajit %A Crutchley, Robert J. %D 2012 %J Inorganic Chemistry %K ESR NMR complex;proton density dicyanamidobenzene functional pentaammine ruthenium theory %N 3 %P 1400--1407 %R 10.1021/ic2016403 %T 1H NMR, Electron Paramagnetic Resonance, and Density Functional Theory Study of Dinuclear Pentaammineruthenium Dicyanamidobenzene Complexes %V 51 %X Paramagnetic 1H NMR and EPR spectroscopies and d. functional theory (DFT) spin d. calcns. were selectively performed on the (NH3)5Ru2(m-L)3+, 4+, 5+ complexes, where L is 2,3,5,6-tetrachloro-, 2,5-dichloro-, 2,5-dimethyl-, and unsubstituted 1,4-dicyanamidobenzene dianion, to characterize the electronic structure of these complexes. EPR spectra of the (NH3)5Ru2(m-L)3+ complexes in N,N'-DMF at 4 K showed a Ru axial signal, and thus the complexes are Ru(II),L2-, Ru(III) mixed-valence systems. DFT spin d. calcns. of (NH3)5Ru2(m-L)3+ where L = 1,4-dicyanamidobenzene dianion gave mostly bridging-ligand centered spin distribution for both vacuum and implicit solvent calcns., in poor agreement with EPR, but more realistic results were obtained when explicit electrostatic interactions between solute and solvent were included in modeling. For the (NH3)5Ru2(m-L)4+ complexes, EPR spectroscopy showed no signal down to 4 K. Nevertheless, solvent-dependent 1H NMR data and anal. support a Ru(III),L2-, Ru(III) state. Hyperfine coupling consts. (Ac/h) of trans- and cis-ammine and Ph hydrogens are 17.2, 3.8, and -1.5 MHz, resp. EPR studies of the (NH3)5Ru2(m-L)5+ complexes showed a metal-radical axial signal and based on previously published 1H NMR data, a Ru(IV),L2-, Ru(III) state is favored over a Ru(III),L-, Ru(III) state. on SciFinder(R)

@article{Naklicki.2012, abstract = {Paramagnetic 1H NMR and EPR spectroscopies and d. functional theory (DFT) spin d. calcns. were selectively performed on the [{(NH3)5Ru}2(\textgreek{m}-L)]3+, 4+, 5+ complexes, where L is 2,3,5,6-tetrachloro-, 2,5-dichloro-, 2,5-dimethyl-, and unsubstituted 1,4-dicyanamidobenzene dianion, to characterize the electronic structure of these complexes. EPR spectra of the [{(NH3)5Ru}2(\textgreek{m}-L)]3+ complexes in N,N'-DMF at 4 K showed a Ru axial signal, and thus the complexes are [Ru(II),L2-, Ru(III)] mixed-valence systems. DFT spin d. calcns. of [{(NH3)5Ru}2(\textgreek{m}-L)]3+ where L = 1,4-dicyanamidobenzene dianion gave mostly bridging-ligand centered spin distribution for both vacuum and implicit solvent calcns., in poor agreement with EPR, but more realistic results were obtained when explicit electrostatic interactions between solute and solvent were included in modeling. For the [{(NH3)5Ru}2(\textgreek{m}-L)]4+ complexes, EPR spectroscopy showed no signal down to 4 K. Nevertheless, solvent-dependent 1H NMR data and anal. support a [Ru(III),L2-, Ru(III)] state. Hyperfine coupling consts. (Ac/h) of trans- and cis-ammine and Ph hydrogens are 17.2, 3.8, and -1.5 MHz, resp. EPR studies of the [{(NH3)5Ru}2(\textgreek{m}-L)]5+ complexes showed a metal-radical axial signal and based on previously published 1H NMR data, a [Ru(IV),L2-, Ru(III)] state is favored over a [Ru(III),L-, Ru(III)] state. [on SciFinder(R)]}, added-at = {2019-07-15T13:41:23.000+0200}, author = {Naklicki, Mark L. and Gorelsky, Serge I. and Kaim, Wolfgang and Sarkar, Biprajit and Crutchley, Robert J.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/20dba78ce9739def7349eeee2db0ae6da/b_schwederski}, doi = {10.1021/ic2016403}, interhash = {5441532b7cf44b6f7530616c6c5e1be7}, intrahash = {0dba78ce9739def7349eeee2db0ae6da}, issn = {0020-1669}, journal = {Inorganic Chemistry}, keywords = {ESR NMR complex;proton density dicyanamidobenzene functional pentaammine ruthenium theory}, number = 3, pages = {1400--1407}, timestamp = {2019-07-15T11:42:10.000+0200}, title = {1H NMR, Electron Paramagnetic Resonance, and Density Functional Theory Study of Dinuclear Pentaammineruthenium Dicyanamidobenzene Complexes}, volume = 51, year = 2012 }