[Molybdenum(VI)/aminopyridinium] system as catalyst for the epoxidation of cyclooctene with H2O2

Abstract A new inorganic–organic supramolecular polymer, i.e. [MoO2Cl2(H2O)2]·Hdpa·Cl·H2O (1) (where Hdpa stands for 2,2′-dipyridylammonium), has been synthesised and characterized, including by single-crystal X-ray diffraction studies. 1 is constituted of inorganic [MoO2Cl2(H2O)2] moieties associated to organic Hdpa units via hydrogen bonds. The combination of hydrogen-bonding and π–π stacking interactions gives rise to a remarkable 3D framework. Compound 1 is an effective catalyst for the H2O2-mediated epoxidation of cyclooctene at 50 °C.

[1]  A. I. Kryukov,et al.  Photolysis of molybdenum(VI) compounds in alcohol matrices , 1983 .

[2]  N. Rao,et al.  Catalytic air oxidation of olefins using molybdenum dioxo complexes with dissymmetric tridentate O,N,S-donor Schiff base ligands derived from o-hydroxyacetophenone and S -benzyldithiocarbazate or S -methyldithiocarbazate , 2007 .

[3]  Michael J. Taylor,et al.  Vibrational and crystallographic studies of dioxohalogenomolybdenum(VI) complexes with crown ethers , 1998 .

[4]  M. Cindrić,et al.  Synthesis of novel molybdenum(V) complexes: Structural characterization of two thiosemicarbazonato complexes [MoOCl2{C6H4(O)CH:NNHC:SNHC6H5}] and [MoOCl2{C10H6(O)CH:NNHC:SNHC6H5}] · CH3CN, and two oxohalomolybdates NH4[MoOCl4(CH3CN)] and [C5H5NH]2[MoOCl5] · CH2Cl2 , 2007 .

[5]  C. G. Young,et al.  Bioinorganic chemistry of pterin-containing molybdenum and tungsten enzymes , 1993 .

[6]  H. Sugimoto,et al.  Chemical analogues relevant to molybdenum and tungsten enzyme reaction centres toward structural dynamics and reaction diversity. , 2008, Chemical Society reviews.

[7]  Y. Luan,et al.  A Two‐Dimensional, Hydrogen‐Bond‐Cross‐Linked Molybdenum(VI) Network Polymer with Catalytic Activity , 2007 .

[8]  R. J. Williams,et al.  The involvement of molybdenum in life. , 2002, Biochemical and biophysical research communications.

[9]  Michael J. Taylor,et al.  Preparation and crystal structure of MoO2Cl2(H2O)2·H2O·Et4NCl in relation to the nature of the molybdenum(VI) species in hydrochloric acid solutions , 1993 .

[10]  C. Carrano,et al.  Oxo-molybdenum(VI,V,IV) complexes of the facially coordinating tris(mercaptoimidazolyl)borate ligand: synthesis, characterization, and oxygen atom transfer reactivity. , 2007, Inorganic chemistry.

[11]  M. Pillinger,et al.  Kinetics of Cyclooctene Epoxidation with tert‐Butyl Hydroperoxide in the Presence of [MoO2X2L]‐Type Catalysts (L = Bidentate Lewis Base) , 2005 .

[12]  W. Levason,et al.  Secondary coordination of dichlorodioxomolybdenum(VI) to crown ethers , 2006 .

[13]  X. Duan,et al.  New molybdenum(VI) catalysts for the epoxidation of cyclohexene: synthesis, reactivity and crystal structures , 2004 .

[14]  J. Klinowski,et al.  Synthesis and catalytic properties in olefin epoxidation of dioxomolybdenum(vi) complexes bearing a bidentate or tetradentate salen-type ligand , 2007 .

[15]  J. Sanz-Aparicio,et al.  Addition compounds of dichlorodioxomolybdenum(VI) from hydrochloric acid solutions of molybdenum trioxide. Crystal structure of dichlorodioxodiaquamolybdenum(VI) bis(2,5,8-trioxanonane) , 1994 .

[16]  Colin Eaborn,et al.  Comprehensive Coordination Chemistry , 1988 .

[17]  A. Capparelli,et al.  Photochemical and catalytic properties of dimeric species of molybdenum(V) , 2000 .

[18]  Richard H. Holm,et al.  Metal-centered oxygen atom transfer reactions , 1987 .

[19]  R. H. Holm The biologically relevant oxygen atom transfer chemistry of molybdenum: from synthetic analogue systems to enzymes , 1990 .

[20]  E. Stiefel The Coordination and Bioinorganic Chemistry of Molybdenum , 2007 .