000196777 001__ 196777
000196777 005__ 20180913062357.0
000196777 0247_ $$2doi$$a10.1021/om400875r
000196777 022__ $$a0276-7333
000196777 02470 $$2ISI$$a000329137900013
000196777 037__ $$aARTICLE
000196777 245__ $$aSynthesis, Characterization, and Reactivity of the First Osmium beta-Diketiminato Complexes and Application in Catalysis
000196777 260__ $$aWashington$$bAmer Chemical Soc$$c2013
000196777 269__ $$a2013
000196777 300__ $$a12
000196777 336__ $$aJournal Articles
000196777 520__ $$aThe strongly chelating anionic beta-diketiminate ligand has been employed to formulate complexes involving almost every metal of the periodic table; however, the heavier metals of the d block remain relatively unexplored. This paper describes the synthesis and characterization of the first two osmium, beta-diketiminato compounds, including a coordinatively unsaturated cationic complex. In parallel to the analogous Ru(II) complexes, the cationic (eta(6)-arene)osmium(II) complex demonstrates bifunctional behavior through [4 + 2] cycloaddition with ethylene, cleavage of dihydrogen under mild conditions, and protonation/chloride addition with [Et2OH]Cl. Metal-centered activity in both the Ru(II) and Os(II) beta-diketiminates has until now remained elusive, as the cationic Os complex is shown to readily coordinate an aryl isonitrile. The applicability of Os(II) beta-diketiminato complexes in catalytic olefin hydrogenation demonstrates significantly greater activity in terms of conversion and TOF for a range of substrates, including styrene, cyclohex-1-ene, and 1-methylcyclohex-1-ene. Moreover, selective hydrogenation of the exocyclic alkenyl group in limonene was observed, whereas the corresponding isostructural Ru(II) complexes are inactive. In contrast, the cationic (eta(6)-arene)ruthenium(II) beta-diketiminato complex proved more active for the catalytic dehydrogenation of N,N-dimethylamine borane (Me2NBH3) than the equivalent Os(II) species. A detailed DFT study of the Ru(II) and Os(II) beta-diketiminato species using charge decomposition analysis (CDA) demonstrates differences in metal ligand interactions, which in turn considerably influences the extent of bifunctional reactivity.
000196777 700__ $$aSchreiber, Dominique F.$$uNatl Univ Ireland Univ Coll Dublin, Sch Chem & Chem Biol, Dublin 4, Ireland
000196777 700__ $$aO'Connor, Crystal$$uNatl Univ Ireland Univ Coll Dublin, Sch Chem & Chem Biol, Dublin 4, Ireland
000196777 700__ $$aGrave, Christian$$uNatl Univ Ireland Univ Coll Dublin, Sch Chem & Chem Biol, Dublin 4, Ireland
000196777 700__ $$aMueller-Bunz, Helge$$uNatl Univ Ireland Univ Coll Dublin, Sch Chem & Chem Biol, Dublin 4, Ireland
000196777 700__ $$0240189$$aScopelliti, Rosario$$g148592
000196777 700__ $$0240015$$aDyson, Paul J.$$g149418
000196777 700__ $$0240014$$aPhillips, Andrew D.$$g172328$$uNatl Univ Ireland Univ Coll Dublin, Sch Chem & Chem Biol, Dublin 4, Ireland
000196777 773__ $$j32$$k24$$q7345-7356$$tOrganometallics
000196777 909C0 $$0252010$$pLCOM$$xU9
000196777 909CO $$ooai:infoscience.tind.io:196777$$pSB$$particle
000196777 917Z8 $$x240314
000196777 937__ $$aEPFL-ARTICLE-196777
000196777 973__ $$aEPFL$$rREVIEWED$$sPUBLISHED
000196777 980__ $$aARTICLE