Binuclear copper(II) complexes with N3S-coordinate tripodal ligand and mixed azide-carboxylate bridges: Synthesis, crystal structures and magnetic properties. (28th January 2017)

• Record Type: Journal Article
• Authors: Sadhu, Mehul H.; Mathoniere, Corine; Patil, Yogesh P.; Kumar, Sujit Baran
• Is Part Of: Polyhedron. Volume 122(2017)
• Page Start: 210
• Page End: 218
• Publication Date: 2017-01-28
• Subjects: N3S donor ligand -- Binuclear Cu(II) complexes -- Bridging ligands -- Structure -- Magnetic studies; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2016.11.036
• Languages: English
• ISSNs: 0277-5387

Abstract

Graphical abstract: One new N3 S-coordinate tetradentate ligand N, N -bis((3, 5-dimethyl-1 H -pyrazol-1-yl)methyl)-2-(phenylthio)ethan-1-amine (bdmpe), two double end-on azide bridged copper(II) complexes [Cu(bdmpe)(μ1, 1 -N3 )]2 (X)2 [X = ClO4 −, PF6 − ] and two triple bridged copper(II) complexes [Cu2 (dmpe)2 (μ1, 1 -N3 )2 (Y)]PF6 [where, dmpe = N -((3, 5-dimethyl-1 H -pyrazol-1-yl)methyl)-2-(phenylthio)ethan-1-amine, Y = CH3 COO − or HCOO − ] have been synthesized and characterized. Crystal structure of the three complexes [Cu(bdmpe)(μ1, 1 -N3 )]2 (ClO4 )2 (1), [Cu2 (dmpe)2 (μ1, 1 -N3 )2 (CH3 COO)]PF6 (3) and [Cu2 (dmpe)2 (μ1, 1 -N3 )2 (HCOO)]PF6 (4) have been solved by single crystal X-ray diffraction studies. Variable temperature (4–273 K) magnetic measurement have been discussed in detail. Abstract: One new N3 S-coordinate tetradentate ligand N, N -bis((3, 5-dimethyl-1 H -pyrazol-1-yl)methyl)-2-(phenylthio)ethan-1-amine (bdmpe) has been synthesized and characterized. Two double end-on azide bridged copper(II) complexes [Cu(bdmpe)(μ1, 1 -N3 )]2 (X)2 [X = ClO4 −, PF6 − ] and two triple bridged copper(II) complexes [Cu2 (dmpe)2 (μ1, 1 -N3 )2 (Y)]PF6 [where dmpe = N -((3, 5-dimethyl-1 H -pyrazol-1-yl)methyl)-2-(phenylthio)ethan-1-amine, Y = CH3 COO − or HCOO − ] have been synthesized and characterized. Ligand (dmpe) has been formed from ligand bdmpe during in situ complexation reaction. Crystal structures of the three complexes [Cu(bdmpe)(N3 )]2 (ClO4 )2 (1 ), [Cu2 (dmpe)2 (μ1, 1 -N3 )2 (CH3 COO)]PF6 (3 ) and [Cu2 (dmpe)2 (μ1, 1 -N3 )2 (HCOO)]PF6 (4 ) have been solved by single crystal X-ray diffraction studies and the structural data revealed that the complex [Cu2 (bdmpe)2 (N3 )2 ](ClO4 )2 is binuclear and two copper(II) centers are bridged by a pair of (μ1, 1 ) N3 − ion whereas the structures of complexes3 and4 are binuclear with triple bridged and two adjacent copper(II) centers are bridged by pair of N3 − ions with end-on (μ1, 1 ) coordination mode and one acetate/formate group with syn–syn coordination mode, respectively. Variable temperature (4–273 K) magnetic measurement shows that complex1 has no magnetic interaction whereas complexes3 and4 have weak antiferromagnetic interactions with J values −15.3(1) cm −1 for complex3 and −17.8(1) cm −1 for complex4 .