Immobilisation of eta(3)-allyidicarbonyl complexes of Mo-II with bidentate nitrogen ligands within aluminium-pillared clays

authors	Alonso, JC; Neves, P; Silva, C; Valente, AA; Brandao, P; Quintal, S; de Brito, MJV; Pinto, P; Felix, V; Drew, MGB; Pires, J; Carvalho, AP; Calhorda, MJ; Ferreira, P
nationality	International
journal	EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
author keywords	molybdenum complexes; N ligands; clays; epoxidation
keywords	TERT-BUTYL HYDROPEROXIDE; DIOXOMOLYBDENUM(VI) COMPLEXES; EPOXIDATION CATALYSTS; MOLYBDENUM COMPLEXES; DERIVATIVES; ENCAPSULATION; DICARBONYL; ADSORPTION; PRECURSORS; KINETICS
abstract	Molybdenum(II) complexes [MOX(CO)(2)(eta(3)-allyl)(CH3CN)(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 Al-27 and Si-29 MAS NMR were used to investigate the integrity of the pillared clay during the modification treatments. C-13 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)(eta(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. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).
publisher	WILEY-V C H VERLAG GMBH
issn	1434-1948
year published	2008
issue	7
beginning page	1147
ending page	1156
digital object identifier (doi)	10.1002/ejic.200700939
web of science category	Chemistry, Inorganic & Nuclear
subject category	Chemistry
unique article identifier	WOS:000254582200021