Synthesis and Structure of Metallocene-type Ti(III) Complexes, and Their Catalytic Activity towards Olefin Hydrosilylation Reactions

Several metallocene-type Ti(III) complexes have been synthesized and structurally determined by single-crystal X-ray diffraction studies. The catalytic activity of the prepared Ti(III) complexes towards olefin hydrosilylation was examined. Mechanistic studies supported a reaction path, which is initiated by the formation of a silyl intermediate via reaction of a Ti(III) methyl catalyst precursor with a hydrosilane.

[1]  Y. Nakajima,et al.  Hydrosilylation reaction of olefins: recent advances and perspectives , 2015 .

[2]  Srinivas Anga,et al.  Titanium and zirconium complexes of the N,N'-bis(2,6-diisopropylphenyl)-1,4-diaza-butadiene ligand: syntheses, structures and uses in catalytic hydrosilylation reactions. , 2014, Dalton transactions.

[3]  M. Drees,et al.  Mechanistic insights into the hydrosilylation of allyl compounds – Evidence for different coexisting reaction pathways , 2012 .

[4]  J. Stohrer,et al.  Recent advances and actual challenges in late transition metal catalyzed hydrosilylation of olefins from an industrial point of view , 2011 .

[5]  D. Guillaneux,et al.  Investigation of titanium-catalysed dehydrogenative coupling and hydrosilylation of phenylhydrogenosilanes in a one-pot process , 2009 .

[6]  W. Baumann,et al.  Ring-Opening Reactions of Tetrahydrofuran versus Alkyne Complexation by Group 4 Metallocene Complexes Leading to General Consequences for Synthesis and Reactions of Metallocene Complexes , 2007 .

[7]  A. K. Roy.  A Review of Recent Progress in Catalyzed Homogeneous Hydrosilation (Hydrosilylation) , 2007 .

[8]  L. Jerzykiewicz,et al.  Structural characterization of a methylaluminoxane (MAO)-magnesium dichloride cluster: model of MAO grafted onto a MgCl2 support. , 2005, Inorganic chemistry.

[9]  B. Marciniec.  Catalysis by transition metal complexes of alkene silylation – recent progress and mechanistic implications , 2005 .

[10]  Laurianne Bareille,et al.  First Titanium-Catalyzed anti-1,4-Hydrosilylation of Dienes , 2005 .

[11]  H. Maciejewski,et al.  Catalytic reactions of hydrosiloxanes with allyl chloride , 2005 .

[12]  B. Tinant,et al.  Selective and Efficient Platinum(0)-Carbene Complexes As Hydrosilylation Catalysts , 2002, Science.

[13]  G. Molander,et al.  Lanthanocene catalysts in selective organic synthesis. , 2002, Chemical reviews.

[14]  T. Tilley,et al.  Hydrosilylation Catalysis by C2-Symmetric Bis(silylamido) Complexes of Yttrium , 1999 .

[15]  J. Stein,et al.  In Situ Determination of the Active Catalyst in Hydrosilylation Reactions Using Highly Reactive Pt(0) Catalyst Precursors , 1999 .

[16]  G. Molander,et al.  INVESTIGATION OF THE REGIOSELECTIVITY OF ALKENE HYDROSILYLATION CATALYZED BY ORGANOLANTHANIDE AND GROUP 3 METALLOCENE COMPLEXES , 1998 .

[17]  H. Schnöckel,et al.  AN UNEXPECTED STRUCTURAL PRINCIPLE FOR CRYSTALLINE MGBR2.OET2 : CHAINS OF TRIGONAL BIPYRAMIDS , 1996 .

[18]  S. Buchwald,et al.  Highly Enantioselective Imine Hydrosilylation Using (S,S)-Ethylenebis(η5-tetrahydroindenyl)titanium Difluoride , 1996 .

[19]  T. Marks,et al.  Regioselection and Enantioselection in Organolanthanide-Catalyzed Olefin Hydrosilylation. A Kinetic and Mechanistic Study , 1995 .

[20]  M. Parra-Hake,et al.  Low Oxidation Dinuclear Titanium Complexes with the Bridging .mu.-(Dimethylsilyl)biscyclopentadienyl Ligand. Crystal Structure of [{Ti(.eta.5-C5H5)}2(.mu.-Cl)2{.mu.-Me2Si(C5H4)2}] , 1995 .

[21]  B. Marciniec,et al.  Recent advances in catalytic hydrosilylation , 1993 .

[22]  J. Y. Corey,et al.  Reactions of Hydrosilanes and Olefins in the Presence of Cp2MCl2/nBuLi , 1992 .

[23]  P. Fanwick,et al.  Zirconium-catalyzed, highly regioselective hydrosilation reaction of alkenes and X-ray structures of silyl(hydrido)zirconocene derivatives , 1991 .

[24]  H. J. Heeres,et al.  Synthesis and Reactivity of Tervalent Paramagnetic Titanium Compounds (η5-C5Me5)2TiR: Molecular Structure of (η5-C5Me5)2TiCH2CMe3 , 1991 .

[25]  S. Yun,et al.  Silyltitanocene complexes as catalysts for the hydrogenation, isomerization, and hydrosilylation of olefins , 1987 .

[26]  A. Spek,et al.  Monomeric Bis(pentamethylcyclopentadienyl)titanium(III) Complexes with Halide, Borohydride, Amide, Alkoxide, and Carboxylate Ligands: X-ray Structure of Bis(pentamethylcyclopentadienyl)titanium(III) Chloride , 1987 .

[27]  R. Jungst,et al.  Structural and magnetic properties of di-.mu.-chloro-bis[bis(.eta.5-cyclopentadienyl)titanium(III)] and di-.mu.-bromo-bis[bis(.eta.5-methylcyclopentadienyl)titanium(III)] , 1977 .