000161646 001__ 161646
000161646 005__ 20190408214830.0
000161646 02470 $$2ISI$$a000208164703235
000161646 037__ $$aCONF
000161646 245__ $$aExperimental and theoretical studies on the mechanism of hydrogenation by η6-arene β-diketiminato -ruthenium and -osmium complexes
000161646 269__ $$a2010
000161646 260__ $$c2010
000161646 336__ $$aConference Papers
000161646 520__ $$aThe β-diketiminate class of ligands is renowned for the stabilization of coordinatively unsatd. main-group and transition metal complexes. Moreover, the application and scope of transition metal β-diketiminate complexes in the catalytic transformation of org. substrates is rapidly increasing. We recently reported on the synthesis, characterization and hydrogenation capabilities of a series of cationic η6-arene Ru- and Os-β-diketiminate complexes, 1. This family of complexes readily undergoes thermo-reversible [4+2] cycloaddn. with alkenes, 2 alkynes and H2 3. DFT calcns., in adjunction with high pressure NMR-deuterium labeling expts., reveal a concerted heterolytic cleavage mechanism with a low energy barrier. Now, a complete mechanistic pathway for alkene hydrogenation for complexes such as 1 has been modeled and supported by exptl. results. Furthermore, in situ NMR studies show that η6-arene hydrogenation is essential for the formation of the active catalytic species. Through steric and electronic variation of both the arene and β-diketiminate ligand, the efficiency of styrene, cyclohexene and 1-methylcyclohexene hydrogenation has been shown to be tunable, with a high turnover rate obsd. Lastly the dehydrogenation application of this family of complexes towards other types of catalysis and substrates will be discussed.
000161646 700__ $$0240014$$g172328$$aPhillips, Andrew D.
000161646 700__ $$aSchreiber, Dominique
000161646 700__ $$aDyson, Paul J.$$g149418$$0240015
000161646 773__ $$tAbstracts of Papers, 240th ACS National Meeting, Boston, MA, United States, August 22-26, 2010
000161646 909CO $$pSB$$pconf$$ooai:infoscience.tind.io:161646
000161646 909C0 $$xU9$$0252010$$pLCOM
000161646 917Z8 $$x179141
000161646 937__ $$aEPFL-ARTICLE-161646
000161646 973__ $$rREVIEWED$$sPUBLISHED$$aEPFL
000161646 980__ $$aCONF