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Molecular hydrides of divalent ytterbium supported by a macrocyclic ligand: synthesis, structure and olefin hydrofunctionalization catalysis.
Chem Commun (Camb)
October 2018
Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52056 Aachen, Germany.
Bis(triphenylsilyl) and dibenzyl ytterbium(ii) complexes supported by the macrocyclic polyamine ligand Me4TACD (1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane) reacted with H2 to give the cationic ytterbium hydrides [(Me4TACD)2Yb2(μ2-H)(2+n)](2-n)+ (n = 0, 1). The hydrides catalyzed the H2/D2 isotope exchange as well as hydrogenation and hydrosilylation of 1-hexene.
View Article and Find Full Text PDFMolecular Calcium Hydride: Dicalcium Trihydride Cation Stabilized by a Neutral NNNN-Type Macrocyclic Ligand.
Angew Chem Int Ed Engl
April 2016
Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52056, Aachen, Germany.
Hydrogenolysis of bis(triphenylsilyl)calcium containing the neutral NNNN-type macrocyclic amine ligand Me4TACD [Ca(Me4TACD)(SiPh3)2] (2), gave the cationic dinuclear calcium hydride [Ca2H3(Me4TACD)2](SiPh3) (3), characterized by NMR spectroscopy, single-crystal X-ray analysis, and DFT calculations. Compound 3 reacted with deuterium to give the deuteride [D3]-3.
View Article and Find Full Text PDFFormation of a Cationic Calcium Hydride Cluster with a "Naked" Triphenylsilyl Anion by Hydrogenolysis of Bis(triphenylsilyl)calcium.
Inorg Chem
May 2015
Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52056 Aachen, Germany.
Protonolysis of bis(triphenylsilyl)calcium [Ca(SiPh3)2(THF)4] (1; THF = tetrahydrofuran) with the NNNN-type macrocyclic amido triamine (Me3TACD)H (TACD = 1,4,7-triazacyclododecane) gave the heteroleptic calcium complex [Ca(Me3TACD)SiPh3] (2) in quantitative yield. Hydrogenolysis of 2 gave the cationic tricalcium dihydride cluster [Ca3H2(Me3TACD)3](+)(SiPh3)(-)·2THF (4a) in high yield with concomitant formation of HSiPh3. In the crystal, 4a consists of a cluster cation and a free triphenylsilyl anion.
View Article and Find Full Text PDFStructures and reactivities of 2-Trityl- and 2-(Triphenylsilyl)pyrrolidine-derived enamines: evidence for negative hyperconjugation with the trityl group.
J Am Chem Soc
October 2014
Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstrasse 5-13, 81377 München, Germany.
X-ray structures of enamines and iminium ions derived from 2-tritylpyrrolidine (Maruoka catalyst) and 2-(triphenylsilyl)pyrrolidine (Bolm-Christmann-Strohmann catalyst) have been determined. Kinetic investigations showed that enamines derived from phenylacetaldehyde and pyrrolidine (R = H) or 2-(triphenylsilyl)pyrrolidine (R = SiPh3) have similar reactivities toward benzhydryl cations Ar2CH(+) (reference electrophiles), while the corresponding enamine derived from 2-tritylpyrrolidine (R = CPh3) is 26 times less reactive. The rationalization of this phenomenon by negative hyperconjugative interaction of the trityl group with the lone pair of the enamine nitrogen is supported by the finding that the trityl group in the 2-position of the pyrrolidine increases the electrophilic reactivity of iminium ions derived from cinnamaldehyde by a factor of 14.
View Article and Find Full Text PDFHighly efficient photocatalytic water reduction with robust iridium(III) photosensitizers containing arylsilyl substituents.
Angew Chem Int Ed Engl
October 2013
Center for Supramolecular Optoelectronic Materials, WCU Hybrid Materials Program and Department of Materials Science and Engineering, Seoul National University, Seoul 151-744 (Korea) http://csom.snu.ac.kr.
Waterproof complexes: Cationic Ir(III) photosensitizers (PSs) with an ancillary 4,4'-bis(4-(triphenylsilyl)phenyl)-2,2'-bipyridine ligand enabled hydrogen evolution from water with high turnover numbers (TONs; see scheme). The peripheral triphenylsilyl moieties prevent ligand substitution by solvent molecules, such as water, and thus increase the durability of the complexes. SR=sacrificial reducing agent, WRC=water-reduction catalyst.
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