期刊
INORGANICA CHIMICA ACTA
卷 363, 期 13, 页码 3390-3398出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/j.ica.2010.06.041
关键词
Manganese; Schiff base; Pentagonal bipyramidal; Phosphine; Ethyldiazoacetate; Imine
资金
- Ohio University
- US National Science Foundation [DBI-0648757]
Manganese(II) complexes [Mn(L)X(2)] were prepared and characterized, where L is a neutral di-Schiff base ligand incorporating pyridylimine donor arms, including (1R,2R)-N,N'-bis(2-pyridylmethylidene)-1,2-diphenylethylenediimine (L(1)), (1R,2R)-N,N'-bis(6-methyl-2-pyridylmethylidene)-1,2-cyclohexyldiimine (L(2)), or (1R,2R)-, (1S,2S)- or racemic N,N'-bis(2-pyridylmethylidene)-1,2-cyclohexyldiimine (L(3)), and X = ClO(4)(-) or Cl. Product complexes were structurally characterized, specifically including [Mn(R,R-L(1))(NCCH(3))(3)](ClO(4))(2), [Mn(R,R-L(2))(OH(2))(2)](ClO(4))(2) and racemic [Mn(L(3))Cl(2)]. The first of these complexes features a heptacoordinate ligand field in a distorted pentagonal bipyramid, and the latter two are hexacoordinate, but retain equatorially monovacant pentagonal bipyramidal structures. Complexes [Mn(L(3))X(2)] (X = Cl, ClO(4)(-)) were reacted with the primary phosphine FeCH(2)PH(2) (Fe = -C(5)H(4)FeC(5)H(5)), H(2)O and ethyldiazoacetate (EDA). The first two substrates prompted reactivity at a single ligand imine bond, resulting in hydrophosphination and hydrolysis, respectively. Complexes of the derivative ligands were also structurally characterized. Evidence for EDA activation was obtained by electrospray ionization mass spectrometry, but catalytic carbene transfer was not obtained. (C) 2010 Elsevier B.V. All rights reserved.
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