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. (1)H NMR spectroscopy and deuterium labeling experiments confirmed the selective cleavage of dihydrogen by the highly polar Ca-Si bond in 1.
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Cyano(triphenylsilyl)phosphanide as a Building Block for P,C,N Conjugated Molecules.
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Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog Weg 1, Hönggerberg, 8093 Zürich, Switzerland.
The cyano(triphenylsilyl)phosphanide anion was prepared as a sodium salt from 2-phosphaethynolate. The electronic structure of this new cyano(silyl)phosphanide was studied via computational methods and its reactivity investigated using various electrophiles and Lewis acids, demonstrating its P- and N-nucleophilicity. The ambident reactivity is in agreement with computations.
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ChemSusChem
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Center for Supramolecular Optoelectronic Materials, Department of Materials Science and Engineering, Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul, 151-744, Korea.
Herein we report a Pt(II) complex containing a 4,4'-bis[4-(triphenylsilyl)phenyl]-2,2'-bipyridine ligand as a molecular catalyst for water splitting. Systematic studies of the electrochemical and electronic properties of this catalyst, in comparison with two control complexes, reveal electron-reservoir characteristics upon two-electron reduction. A turnover number of 510,000 was recorded by employing this complex as a water reduction catalyst in combination with a state-of-the-art photosensitizer and N,N-dimethylaniline as a sacrificial electron donor, which represents a large improvement over the control complexes that do not contain the tetraphenylsilyl ligand substitution.
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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.
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Institute of Organic Chemistry, University of Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany.
Starting from 2-(triphenylsilyl)ethanol a new oxycarbonyl protecting group cleavable by fluoride ion induced Peterson-elimination has been developed. Known 2-(triphenylsilyl)ethanol has been prepared from commercially available triphenylvinyl-silane by a hydroboration-oxidation sequence using the sterically hindered borane reagent 9-BBN. The silyl alcohol was subsequently transformed into its chloroformate, imidazolylcarboxylic acid ester and p-nitrophenyl carbonate and used in standard protocols for the formation of carbamates and carbonates.
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Inorg Chem
January 2002
Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USA.
The structural coordination chemistry of the sterically hindered 3,3'-bis(triphenylsilyl)-1,1'-bi-2-phenoxide ligand ([(TPS)LO(2)](2)(-)), an isosteric homologue of a chiral binaphthoxide ligand used in asymmetric induction, has been investigated on Fe(II), Fe(III), and Cr(II). The ligand diol ((TPS)L(OH)(2), 2) can be prepared on a multigram scale from 2,2'-dimethoxybiphenyl via a convenient, two-step ortho-metalation/silylation/deprotection sequence; the sodium salt of the ligand dianion (Na(2)[(TPS)LO(2)], 3) can be obtained by NaH deprotonation and was crystallographically characterized with two THF ligands bound to each cation. Protonolysis of Fe[N(SiMe(3))(2)](2) or Cr[N(SiMe(3))(2)](2)(THF)(2) with biphenol 2 in arene solvent gives [Fe(mu-(TPS)LO(2))](2) (4) or ((TPS)LO(2))Cr(THF)(2) (9), respectively, while anion metathesis of FeCl(2) or FeCl(3)/bipy with biphenoxide salt 3 in THF yields ((TPS)LO(2))Fe(THF)(2) (8) or ferric monomer ((TPS)LO(2))FeCl(bipy) (10), respectively.
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