Abstract

A new mononuclear dioxomolybdenum(VI) complex, [MoO2L1], and a new linear trinuclear nickel(II) complex, [NiNiL2(?1-?1:?0-OAc)(?2-?1:?1-OAc)2]·H2O, where L1 is the dianionic form of N,N'-bis(5-fluorosalicylidene)-1,3-propanediamine (H2L1), L2 is the dianionic form of N,N'-bis(5-fluoro-2-hydroxybenzylidene)-2-hydroxy-1,3-propanediamine (H2L2), have been synthesized and characterized by elemental analysis, FT-IR spectroscopy, and single-crystal X-ray determination. The Mo atom in the molybdenum complex is coordinated by four donor atoms of the Schiff base ligand, and two oxo groups, forming an octahedral coordination. In the nickel complex, there are three bridges across the Ni-Ni atom pairs, involving two phenolate O atoms of a Schiff base ligand, and an O-C-O moiety of a ?2-?1:?1-OAc group. The central Ni atom is located on an inversion center and has octahedral coordination involving four bridging O atoms from two Schiff base ligands in the equatorial plane and two O atoms from two ?2-?1:?1-OAc ligands in the axial positions. The coordination around the terminal Ni atoms is also octahedral, with two imino N and two phenolate O atoms from a Schiff base ligand defining the equatorial plane, and with two O atoms respectively from a ?1-?1:?0-OAc and a ?2-?1:?1-OAc ligands occupying the axial positions. The molybdenum complex has excellent catalytic property for sulfoxidation reactions.

Highlights

  • Molybdenum and nickel complexes with multi-dentate ligands have received remarkable attention in recent years for their catalytic properties[1] and molecular structures.[2]

  • We report in this paper the syntheses, crystal structures and catalytic property of a new dioxomolybdenum(VI) complex, [MoO2L1], and a new linear trinuclear nickel(II) complex, [Ni{NiL2 (μ1-η1:η0-OAc)(μ2-η1:η1-OAc)}2] · H2O, where L1 is the dianionic form of N,N’-bis(5-fluorosalicylidene)-1,3-propanediamine (H2L1), L2 is the dianionic form of N,N’bis(5-fluoro-2-hydroxybenzylidene)-2-hydroxy-1,3-propanediamine (H2L2; Scheme 1)

  • Atoms O(1), N(1), N(2) and O(3) located at the equatorial plane show a high degree of planarity, with mean deviation from the plane of 0.002(3) Å

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Summary

Introduction

Molybdenum and nickel complexes with multi-dentate ligands have received remarkable attention in recent years for their catalytic properties[1] and molecular structures.[2]. Reaction of the Schiff base H2L1 with MoO2(acac)[2], and H2L2 with Ni(CH3COO)[2], respectively, afforded the molybdenum and nickel complexes. The coordination geometry around the Mo atom in the complex is octahedrally distorted.

Results
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