35933
2012
2012
eng
965
975
11
6
638
article
Wiley-VCH
Weinheim
1
--
--
--
EPR spectroscopy of 4, 4 '-Bis(tert-butyl)-2, 2 '-bipyridine-1, 2-dithiolatocuprates(II) in host lattices with different coordination geometries
A series of new heteroleptic MN2S2 transition metal complexes with M = Cu2+ for EPR measurements and as diamagnetic hosts Ni2+, Zn2+, and Pd2+ were synthesized and characterized. The ligands are N2 = 4, 4'-bis(tert-butyl)-2, 2'-bipyridine (tBu2bpy) and S2 =1, 2-dithiooxalate, (dto), 1, 2-dithiosquarate, (dtsq), maleonitrile-1, 2-dithiolate, or 1, 2-dicyanoethene-1, 2-dithiolate, (mnt). The CuII complexes were studied by EPR in solution and as powders, diamagnetically diluted in the isostructural planar [NiII(tBu2bpy)(S2)] or[PdII(tBu2bpy)(S2)] as well as in tetrahedrally coordinated[ZnII(tBu2bpy)(S2)] host structures to put steric stress on the coordination geometry of the central CuN2S2 unit. The spin density contributions for different geometries calculated from experimental parameters are compared with the electronic situation in the frontier orbital, namely in the semi-occupied molecular orbital (SOMO) of the copper complex, derived from quantum chemical calculations on different levels (EHT and DFT). One of the hosts, [NiII(tBu2bpy)(mnt)], is characterized by X-ray structure analysis to prove the coordination geometry. The complex crystallizes in a square-planar coordination mode in the monoclinic space group P21/a with Z = 4 and the unit cell parameters a = 10.4508(10) angstrom, b = 18.266(2) angstrom, c = 12.6566(12) angstrom, beta = 112.095(7)degrees. Oxidation and reductions potentials of one of the host complexes, [Ni(tBu2bpy)(mnt)], were obtained by cyclovoltammetric measurements.
Zeitschrift für anorganische und allgemeine Chemie
10.1002/zaac.201100517
0044-2313
wos:2011-2013
WOS:000304528800011
Strauch, P (reprint author), Univ Potsdam, Inst Chem, Karl Liebknecht Str 24-25, D-14476 Potsdam, Germany., pstrauch@uni-potsdam.de
DAAD [A/05/06200]
Duha Jawad Awad
Andreas Koch
Wulfhard Mickler
Uwe Schilde
Peter Strauch
eng
uncontrolled
1
eng
uncontrolled
2-Dithiosquarate
eng
uncontrolled
1
eng
uncontrolled
2-Dithiooxalate
eng
uncontrolled
1
eng
uncontrolled
2-Dicyanoethene-1
eng
uncontrolled
2-dithiolate
eng
uncontrolled
4
eng
uncontrolled
4'-Bis(tert-butyl)-2
eng
uncontrolled
2'-bipyridine
eng
uncontrolled
X-ray structure
eng
uncontrolled
EPR
eng
uncontrolled
Copper
eng
uncontrolled
Nickel
eng
uncontrolled
Zinc
Institut für Chemie
Referiert
37074
2011
2011
eng
127
132
6
1
365
article
Elsevier
Lausanne
1
--
--
--
4,4 '-Bis(tert-butyl)-2,2 '-bipyridinedichlorometal(II) - Synthesis, structure and EPR spectroscopy
Due to the better solubility of the 4,4'-substituted bipyridine ligand a series of 4,4'0-bis(tert-butyl)-2,2'-bipyridinedichlorometal(II) complexes, [M(tbbpy)Cl(2)], with M = Cu, Ni, Zn, Pd, Pt was synthesised and characterised. The blue copper complex 4,4'-bis(tert-butyl)-2,2'-bipyridinedichlorocopper(II) was isolated in two different polymorphic forms, as prisms 1 with a solvent inclusion and solvent-free as needles 2. Both structures were determined by X-ray structure analysis. They crystallise in the monoclinic space group P2(1)/c with four molecules in the unit cell, but with different unit cells and packing motifs. Whereas in the prisms 1, with the unit cell parameters a = 12.1613(12), b = 10.6363(7), c = 16.3074(15) angstrom, eta = 94.446(8)degrees, the packing is dominated by intra-and intermolecular hydrogen bonds, in the needles 2, with a = 7.738(1), b = 18. 333(2), c = 13.291(3) angstrom, beta = 97.512(15)degrees, only intramolecular hydrogen bonds appear and the complex molecules are arranged in columns which are stabilised by p-p-stacking interactions. In both complexes the copper has a tetrahedrally distorted coordination sphere. These copper complexes were also studied by EPR spectroscopy in solution, as frozen glass and diamagnetically diluted powder with the analogue [Pd(tbbpy)Cl(2)] as host lattice.
Inorganica chimica acta : the international inorganic chemistry journal
10.1016/j.ica.2010.08.035
0020-1693
wos:2011-2013
WOS:000285624200019
Strauch, P (reprint author), Univ Potsdam, Inst Chem, Karl Liebknecht Str 24-25, D-14476 Potsdam, Germany., pstrauch@uni-potsdam.de
DAAD [A/05/06200]
Duha Jawad Awad
Uwe Schilde
Peter Strauch
eng
uncontrolled
4,4 '-Bis(tert-butyl)-2,2 '-bipyridine
eng
uncontrolled
X-ray structure
eng
uncontrolled
EPR
eng
uncontrolled
Copper(II)
eng
uncontrolled
Transition metals
Institut für Chemie
Referiert