01704nas a2200193   4500008004100000245019700041210006900238260000800307300001800315490000700333520090500340100002401245700001901269700002501288700002501313700002401338700001901362856012901381       2011                        eng d00aPhotocatalytic splitting of CS2 to a carbon-sulfur polymer and S8 catalyzed by a bimetallic ruthenium(II) compound with a tertiary amine binding site - towards photocatalytic splitting of CO2?0 aPhotocatalytic splitting of CS2 to a carbonsulfur polymer and S8  cOCT  a11273–112750 v503 a<p>The catalytic photocleavage of CS2 to S8 and a (CxSy)n polymer with visible light using a dinuclear ruthenium(II) compound with a bipyridine units for photoactivity and a vicinal tertiary amine binding site for CS2 activation was studied. The catalyst was characterized by X-ray diffraction, 1H NMR, and 13C NMR, ESI-MS and elemental analysis. CS2 photocleavage was significant (240 turnovers, 20 h) to yield isolable S8 and a (CxSy)n polymer. A mononuclear catalyst or one without an amine binding site showed significantly less activity. XPS of the (CxSy)n polymer showed a carbon/sulfur ratio ∼1.5–1.6 indicating that in part both C–S bonds of CS2 had been cleaved. Catalyst was also included within the polymer. The absence of peaks in the 1H NMR verified the (CxSy)n nature of the polymer, while 13C NMR and IR indicated that the polymer had multiple types of C–S and C–C bonds.</p>1 aLivanov, Konstantin1 aMadhu, Vedichi1 aBalaraman, Ekambaram1 aShimon, Linda, J. W.1 aDiskin-Posner, Yael1 aNeumann, Ronny  uhttp://library.ncl.res.in/content/photocatalytic-splitting-cs2-carbon-sulfur-polymer-and-s8-catalyzed-bimetallic-rutheniumii02342nas a2200193   4500008004100000245016200041210006900203260000800272300001600280490000700296520155600303100003301859700002501892700002401917700002001941700002501961700002001986856014202006       2013                        eng d00aPNN-Ru pincer complexes based on phosphinated 2,2’-dipyridinemethane- and 2,2’-oxobispyridine. metal-ligand cooperation in cyclometallation and catalysis0 aPNNRu pincer complexes based on phosphinated 22 dipyridinemethan  cMAY  a2973–29820 v323 a<p>The synthesis of novel PNN ruthenium pincer complexes based on 2,2′-dipyridinemethane phosphine derivatives, as well as on 2,2′-oxobispyridine phosphine ligands, and their reactivity toward dearomatization and cyclometalation are described. The dearomatized compounds 7a,b undergo cyclometalation to yield complexes 8a,b. In order for cyclometalation to proceed, the coordination sphere around the Ru center has to rearrange, and this depends on the flexibility of the system, showing that the cyclometalation is qualitatively faster in the case of the dimethyl derivative 7a than in the case of the spyrocyclopentyl derivative 7b. The cyclometalation occurs diastereoselectively and leads to only one diastereomer of the cyclometalated compounds. In the case of the 2,2′-oxobispyridine complex 6c, the dearomatized complex was too unstable to be isolated; however it was possible to isolate and characterize a stable dicarbonyl-dearomatized ruthenium(II) complex, 9c, when the deprotonation was performed under a CO atmosphere. Dearomatization of 6a under CO also led to dicarbonyl-dearomatized ruthenium(II) complex 9a, which slowly rearranged into the dicarbonyl-aromatized ruthenium(0) complex 10a. These complexes were tested in catalytic alcohol–amine coupling, esterification of primary alcohols, and hydrogenation of secondary amides. Moderate activity was observed in hydrogenation of amides to alcohols and amines and low activity in the other transformations, owing mainly to the formation of stable cyclometalated compounds.</p>1 aBarrios-Francisco, Rigoberto1 aBalaraman, Ekambaram1 aDiskin-Posner, Yael1 aLeitus, Gregory1 aShimon, Linda, J. W.1 aMilstein, David  uhttp://library.ncl.res.in/content/pnn-ru-pincer-complexes-based-phosphinated-22%E2%80%99-dipyridinemethane-and-22%E2%80%99-oxobispyridine