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Immobilisation of η 3 ‐Allyldicarbonyl Complexes of Mo II with Bidentate Nitrogen Ligands within Aluminium‐Pillared Clays
Author(s) -
Alonso João Carlos,
Neves Patrícia,
Silva Carlos,
Valente Anabela A.,
Brandão Paula,
Quintal Susana,
Villa de Brito Maria J.,
Pinto Patrícia,
Félix Vítor,
Drew M. G. B.,
Pires João,
Carvalho Ana Paula,
Calhorda Maria José,
Ferreira Paula
Publication year - 2008
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200700939
Subject(s) - chemistry , denticity , inorganic chemistry , nuclear chemistry , zirconium , nitrogen , cyclooctene , cyclohexene , molybdenum , ligand (biochemistry) , vanadium , crystal structure , medicinal chemistry , crystallography , organic chemistry , catalysis , biochemistry , receptor
Molybdenum(II) complexes [MoX(CO) 2 (η 3 ‐allyl)(CH 3 CN) 2 ] (X = Cl or Br) were encapsulated in an aluminium‐pillared natural clay or a porous clay heterostructure and allowed to react with bidentate diimine ligands. All the materials obtained were characterised by several solid‐state techniques. Powder XRD, and 27 Al and 29 Si MAS NMR were used to investigate the integrity of the pillared clay during the modification treatments. 13 C CP MAS NMR, FTIR, elemental analyses and low‐temperature nitrogen adsorption showed that the immobilisation of the precursor complexes was successful as well as the in situ ligand‐substitution reaction. The new complex [MoBr(CO) 2 (η 3 ‐allyl)(2‐aminodipyridyl)] was characterised by single‐crystal X‐ray diffraction and spectroscopic techniques, and NMR studies were used to investigate its fluxional behaviour in solution. The prepared materials are active for the oxidation of cis ‐cyclooctene using tert ‐butyl hydroperoxide as oxidant, though the activity of the isolated complexes is higher. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)