Copper(II) complexes of open-chain thioether ligands terminated by salicylaldimine functionality*This article has a companion paper in this issue (doi: 10.1139/v11-081).

2011 ◽  
Vol 89 (10) ◽  
pp. 1190-1201 ◽  
Author(s):  
C. Robert Lucas ◽  
John M.D. Byrne ◽  
Julie L. Collins ◽  
Louise N. Dawe ◽  
David O. Miller
Keyword(s):  
Magnetic Susceptibility ◽  
Single Crystal ◽  
Variable Temperature ◽  
Companion Paper ◽  
Structural Studies ◽  
Binuclear Copper ◽  
Open Chain ◽  
X Ray ◽  
Variable Temperature Magnetic Susceptibility ◽  
Coordination Spheres

From 1,11-bis(salicylaldimine)-3,6,9-trithiaundecane (H2L1), 1,11-bis(salicylaldimine)-6-oxa-3,9-dithiaundecane (H2L2), and 1,8-bis(salicylaldimine)-3,6-dithiaundecane (H2L3), syntheses for [Cu(L1)]2 (I), Cu(L2)·CH3OH (II), Cu(L3) (III), [Cu(HL3)][CH3COO] (IV), [Cu(HL1-sal)]Cl2 (V), Cu4(L1)2Br4(H2O)2·2H2O (VI) and Cu2(L2)Br2·xH2O (VII) are described. Single crystal X-ray structural studies for I, III and VII are reported. Variable temperature magnetic susceptibility studies of I, VI and VII are discussed. The examination of VII represents the first magneto-structural study of a binuclear copper(II) species with NSO3Br coordination spheres. This study examines perturbation by one or more of the donor atoms so that none of the known magnetostructural models predicts the copper–copper coupling.

Thiophenophane metal complexes IV. Effects from ligand changes outside the coordination sphere

1996 ◽  
Vol 74 (11) ◽  
pp. 2340-2348 ◽  
Author(s):  
C. Robert Lucas ◽  
Shuang Liu
Keyword(s):  
Magnetic Susceptibility ◽  
Variable Temperature ◽  
Cyclic Voltammograms ◽  
Ferromagnetic Coupling ◽  
X Ray ◽  
H Nmr ◽  
Variable Temperature Magnetic Susceptibility ◽  
Structural Differences ◽  
Coordination Spheres ◽  
Temperature Responses

Preparation of two thiophenophane polythioether macrocycles and 11 of their complexes of Cu(I), Cu(II), Ag(I), and Pd(II) is described. The single crystal X-ray structure of [(CuBr)2(L1)x is reported: space group Pcma, a = 8.7120(6), b = 10.7791(5), c = 12.0929(5) Å, Z = 2, Rf = 0.052, Rw = 0.036 for 521 reflections. Variable-temperature magnetic susceptibility measurements for [(CuCl2)2(L1)] and [(CuCl2)2(L2)] reveal weak antiferromagnetic and weak ferromagnetic coupling, respectively. Cyclic voltammograms of these compounds display two unequal waves in acetonitrile solvent but only one in nitromethane or dimethyl sulfoxide. 1H NMR spectra of {[(η-C3H5)Pd]2(L1)}{PF6}2 and {[(η-C3H5)Pd]2(L2)}{PF6}2 in various solvents show different temperature responses. These magnetic, electrochemical, and NMR effects are discussed in the light of structural differences at sites in the two ligands that are outside the coordination spheres. Key words: magnetic susceptibility, copper, thioether, electrochemistry.

Cobalt and nickel complexes of open-chain thioether ligands terminated by salicylaldimine functionality*This article has a companion paper in this issue (doi: 10.1139/v11-083).

2011 ◽  
Vol 89 (10) ◽  
pp. 1174-1189 ◽  
Author(s):  
C. Robert Lucas ◽  
John M.D. Byrne ◽  
Julie L. Collins ◽  
Louise N. Dawe ◽  
David O. Miller
Keyword(s):  
Single Crystal ◽  
Electronic Spectra ◽  
Nickel Complexes ◽  
Cobalt Complexes ◽  
Companion Paper ◽  
Cyclic Voltammograms ◽  
Structural Studies ◽  
Open Chain ◽  
X Ray ◽  
Cobalt And Nickel

Syntheses of 1,11-bis(salicylaldimine)-3,6,9-trithiaundecane (H2L1), 1,11-bis(salicylaldimine)-6-oxa-3,9-dithiaundecane (H2L2), and 1,8-bis(salicylaldimine)-3,6-dithiaundecane (H2L3), their nickel complexes [Ni(L1)]·H2O (I), [Ni(HL2)][OAc] (II), [Ni(L3)·HOAc]2[Ni(L3)·2HOAc]·3H2O (III), [Ni(HL1-sal)]Cl2·H2O (IV), [Ni(HL2-sal)]Cl2·CH3OH (V), [Ni(L3-sal)Cl]·H2O (VI), {[Ni(HL1-sal)]Br2}2{[Ni(L1-sal)]Br}·H2O (VII), {[Ni(HL2-sal)]Br2}2{[Ni(L2-sal)]Br}·2CH3OH (VIII), {[Ni(HL3-sal)Br]Br}[Ni(L3-sal)Br]·2CH3OH (IX), [Ni(HL3-sal)Br]Br·CH3OH (X), [Ni(HL3)Br]·2H2O (XI), [Ni(HL1)]2[BF4]2·5H2O (XII), [Ni(HL2)]2[BF4]2·3H2O (XIII), [Ni(HL3)]2[BF4]2·CH3CN (XIV), and [Ni(HL3)]2[BF4]2·3H2O (XV) and their cobalt complexes [Co(L1-sal)][BF4]2 (XVI), [Co(L2)][OAc]·3H2O (XVII), [Co(L3)][OAc]·3H2O (XVIII), [Co(L3)][BF4] (XIX), and [Co(L3-sal)(CH3OH)][BF4]2·CH3OH (XX) are reported. Single crystal X-ray structural studies for III, XIV, XVI, and XIX are described. Cyclic voltammograms of the ligands and of I, II, III, VII, VIII, X, XIV, and XIX are discussed. Electronic spectra of the ligands and complexes are discussed.

Manganese(II) Oxazolidine Nitroxide Chelates: Structure, Magnetism, and Redox Properties

2014 ◽  
Vol 67 (11) ◽  
pp. 1618 ◽  
Author(s):  
Ian A. Gass ◽  
Mousa Asadi ◽  
David W. Lupton ◽  
Boujemaa Moubaraki ◽  
Alan M. Bond ◽  
...  
Keyword(s):  
Magnetic Susceptibility ◽  
Intramolecular Interaction ◽  
Variable Temperature ◽  
Field Measurements ◽  
X Ray Diffraction ◽  
Magnetic Susceptibility Data ◽  
X Ray ◽  
Susceptibility Data ◽  
Variable Temperature Magnetic Susceptibility ◽  
Radical Interaction

The mononuclear oxazolidine nitroxide complex [MnII(L•)2](ClO4)2 (1) (L•, 4-dimethyl-2,2-di(2-pyridyl)oxazolidine N-oxide) has been synthesized and investigated using single-crystal X-ray diffraction, variable-temperature magnetic susceptibility measurements, and electrochemistry. The structural analysis reveals bond lengths compatible with a linear L•–MnII–L• arrangement where the ligands are in the neutral ligand form and the central MnII ion is high spin (S = 5/2). Although analysis of the variable-temperature magnetic susceptibility data suggests a strong antiferromagnetic metal–radical interaction, the radical–radical intramolecular interaction could not be determined unambiguously from such fits. The resultant isolated S = 3/2 ground state is confirmed by low-temperature magnetization versus field measurements. Electrochemical studies reveal similar square schemes and redox intermediates to the previously reported analogues [FeII(L•)2][BF4]2 and [CoII(L•)2][NO3]2.

Ternary Antimonides RE4T7Sb6 (RE=Gd–Lu; T =Ru, Rh) with Cubic U4Re7Si6-type Structure

2013 ◽  
Vol 68 (9) ◽  
pp. 971-978 ◽  
Author(s):  
Inga Schellenberg ◽  
Ute Ch. Rodewald ◽  
Christian Schwickert ◽  
Matthias Eul ◽  
Rainer Pöttgen
Keyword(s):  
Magnetic Susceptibility ◽  
Single Crystal ◽  
Magnetic Moment ◽  
Induction Furnace ◽  
X Ray Diffraction ◽  
Temperature Dependent ◽  
X Ray ◽  
Antiferromagnetic Ordering ◽  
Arc Melting ◽  
Intermediate Valent

The ternary antimonides RE4T7Sb6 (RE=Gd-Lu; T =Ru, Rh) have been synthesized from the elements by arc-melting and subsequent annealing in an induction furnace. The samples have been characterized by powder X-ray diffraction. Four structures were refined on the basis of single-crystal X-ray diffractometer data: U4Re7Si6 type, space group Im3m with a=862.9(2) pm, wR2=0.0296, 163 F2 values for Er4Ru7Sb6; a=864.1(1) pm, wR2=0.1423, 153 F2 values for Yb4Ru7Sb6; a=872.0(2) pm, wR2=0.0427, 172 F2 values for Tb4Rh7Sb6; and a=868.0(2) pm, wR2=0.0529, 154 F2 values for Er4Rh7Sb6, with 10 variables per refinement. The structures have T1@Sb6 octahedra and slightly distorted RE@T26Sb6 cuboctahedra as building units. The distorted cuboctahedra are condensed via all trapezoidal faces, and this network leaves octahedral voids for the T1 atoms. The ruthenium-based series of compounds was studied by temperature-dependent magnetic susceptibility measurements. Lu4Ru7Sb6 is Pauli-paramagnetic. The antimonides RE4Ru7Sb6 with RE=Dy, Ho, Er, and Tm show Curie-Weiss paramagnetism. Antiferromagnetic ordering occurs at 10.0(5), 5.1(5) and 4.0(5) K for Dy4Ru7Sb6, Ho4Ru7Sb6 and Er4Ru7Sb6, respectively, while Tm4Ru7Sb6 remains paramagnetic. Yb4Ru7Sb6 is an intermediate-valent compound with a reduced magnetic moment of 3.71(1) μB per Yb as compared to 4.54 μB for a free Yb3+ ion

Comparative Structural Studies on Three-Coordinate Copper(I) Halide Complexes With Tertiary Phosphines. Crystal Structures of [(PPh2Mes)CuX]2 and [(PPhMes2)CuX]2 (Mes = Mesityl X = Cl, Br, I)

1992 ◽  
Vol 45 (7) ◽  
pp. 1155 ◽  
Author(s):  
GA Bowmaker ◽  
D Camp ◽  
RD Hart ◽  
PC Healy ◽  
BW Skelton ◽  
...  
Keyword(s):  
Single Crystal ◽  
Crystal Structures ◽  
Copper Atom ◽  
Structural Studies ◽  
Coordination Environment ◽  
X Ray ◽  
Tertiary Phosphines ◽  
Structure Determinations ◽  
Halide Complexes ◽  
The Subject

The 1 : 1 complexes of the substituted triphenylphosphine ligands mesityldiphenylphosphine and dimesitylphenylphosphine with copper(1) chloride, bromide and iodide have been the subject of single-crystal X-ray structure determinations at 295 K. All six complexes crystallize as air-stable dimeric molecules, [(PPh2Mes)CuX]2 and [ (PPhMes2)CUX]2 with each copper atom in a distorted trigonal PCuX2. coordination environment. Crystals of [(PPh2Mes)CuCl]2 (1) are monoclinic, P21/n, a 9.961(3), b 18.687(6), c 11.009(7) Ǻ, β 114.63(4)°; R was 0.049 for 2450 'observed' reflections. [(PPh2Mes)CuBrI2 (2) is monoclinic, P21/n, a 9.939(2), b 18.832(6), c 11.238(6) Ǻ, β 115.36(3)°; R was 0.046 for 1803 'observed' reflections. [(PPh2Mes)CuI]2.4/3 C6H6 (3) is rhornbohedral, R3, a 36.877(8), c 9.047(5) A; R was 0.039 for 2537 'observed' reflections. Crystals of [(PPhMes2)CuCl]2.2MeCN (4) are triclinic, Pi, a 15.783(7), b 9.570(4), c 8.914(4) Ǻ, α 72.43(3), β 76.37(3), γ 74.03(3)°; R was 0.045 for 3341 'observed' reflections. [(PPhMes2)CuBr]2.3C6H6 (5) is monoclinic, C2/c, a 9.694(6), b 30.15(2), c 20.66(2) Ǻ, β 98.00(7)°; R was 0.047 for 2117 'observed' reflections. [(PPhMes2)CuI]2.2MeCN (6) is orthorhombic, PP1nb, a 11.694(8), b 14.77(1), c 29.76(3) Ǻ; R was 0.049 for 3447 'observed' reflections. Cu-P bond lengths are: 2.196(2) A (1); 2.198(3) Ǻ (2); 2.222(5) and 2.226(5) Ǻ (3); 2.202(1) Ǻ (4); 2.197(3) A (5); 2.201(4) and 2.264(5) Ǻ (6). The geometries of the LCuX2 and CuX2Cu units are compared with data reported for other monomeric and dimeric compounds for both phosphorus- and nitrogen-based ligands L.

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