resumo
The oxo-bridged dinuclear complex [Mo2O4(mu(2)-O)Cl-2(pypzEA)(2)] (2) (pypzEA = ethyl[3-(pyridin-2-yl)-1H-pyrazol-1-yl]acetate) was obtained upon the treatment of [MoO2Cl2(pypzEA)] (1) with ethanol. The molecular structure of 2 consists of two highly distorted {MoClN2O3} octahedra sharing a corner oxygen atom, with a Mo - O -Mo "kink" angle of 163.2(2)degrees and a Mo center dot center dot center dot Mo separation of 3.7029(7) angstrom. Catalytic results with 2 for the epoxidation of cis-cyclooctene using tert-butylhydroperoxide as oxidant compare favorably with those reported for related oxomolybdenum(VI) complexes. The reaction is homogeneous in nature, and a fraction of 2 dissolves and is converted to other types of soluble active species, one of which was isolated and identified as the oxodiperoxo complex [MoO(O-2)(2)(pypzEA)] (3). (C) 2013 Elsevier B.V. All rights reserved.
palavras-chave
BOND-VALENCE PARAMETERS; CYCLOOCTENE EPOXIDATION; CRYSTAL-STRUCTURES; DATABASE; CORE; DIOXO
categoria
Chemistry
autores
Amarante, TR; Gomes, AC; Neves, P; Paz, FAA; Valente, AA; Pillinger, M; Goncalves, IS
nossos autores
Ana Catarina Costa Gomes Alves
Investigador Auxiliar
Anabela Tavares Aguiar Valente
Investigador Principal
Filipe Alexandre Almeida Paz
Investigador Principal
Isabel Maria de Sousa Gonçalves
Professor associado
Martyn Pillinger
Investigador Principal
Patrícia dos Santos Neves
Investigador Auxiliar
Tatiana Ribau Amarante
Investigador Júnioragradecimentos
We are grateful to the Fundacao para a Ciencia e a Tecnologia (FCT), the Programa Operacional Ciencia e Inovacao (POCI) 2010, Orcamento do Estado (OE), Fundo Europeu de Desenvolvimento Regional (FEDER) and CICECO (Pest-C/CTM/LA0011/2011) for funding. The FCT is acknowledged for financial support toward the purchase of the single-crystal diffractometer. We thank the FCT for a PhD grant to TRA (SFRH/BD/64224/2009) and a post-doctoral grant to PN (SFRH/BPD/73540/2010).