Palladium(II) Complexes with Dithiomalonamide and N,N′-Diphenyldithiomalonamide

1974 ◽  
Vol 52 (20) ◽  
pp. 3454-3458 ◽  
Author(s):  
Gian Carlo Pellacani
Keyword(s):  
Electronic Spectra ◽  
Bidentate Ligand ◽  
Membered Ring ◽  
Orbital Parameters ◽  
Square Planar ◽  
Anionic Ligands ◽  
Ligand Coordination ◽  
Ring Complexes ◽  
Square Planar Complexes ◽  
Spectrochemical Series

Dithiomalonamide (Hdtma) and N,N′-diphenyldithiomalonamide (Hdpma) form diamagnetic square-planar complexes PdL2 and PdL2•2DMF. For these complexes a [PdS4] coordination was suggested by their electronic and i.r. spectra. The splitting orbital parameters, Δ1, indicates that these anionic ligands assume an intermediate position in the spectrochemical series of sulfur donors. These ligands also form Pd(HL)2X2 (X = Cl, Br, I, ClO4) and PdHLX2 (X = Cl, Br, I) complexes in which spectroscopic evidence suggests an S,N bidentate ligand coordination, forming six-membered rings. ν(PdN) and ν(PdS) are tentatively assigned. For Pd(Hdpma)2X2 complexes from the far i.r. and electronic spectra we propose a cis-PdN2S2 configuration. The Δ1 parameters in the six-membered ring Pd(HL)2X2 complexes indicate a ligand strength greater than in the analogous S,N coordinated five-membered ring complexes of dithiooxamides and show an inversion of the order found in Ni(HL)2X2 (HL = Hdtma, Hdpma) complexes. In PdHLX2 complexes the presence of two bands assignable to Vasym(PdX) and Vsym(PdX) supports a cis-halogen configuration.

scholarly journals Diaquabis[4-(dimethylamino)benzoato](isonicotinamide)zinc(II)

2009 ◽  
Vol 65 (6) ◽  
pp. m651-m652 ◽  
Author(s):  
Tuncer Hökelek ◽  
Hakan Dal ◽  
Barış Tercan ◽  
Özgür Aybirdi ◽  
Hacali Necefoğlu
Keyword(s):  
Dihedral Angle ◽  
Bidentate Ligand ◽  
Membered Ring ◽  
Carboxyl Groups ◽  
Water Molecules ◽  
Distorted Octahedral Coordination ◽  
Square Planar ◽  
Distorted Octahedral ◽  
Benzene Rings ◽  
Monodentate Ligands

The molecule of the title ZnIIcomplex, [Zn(C9H10NO2)2(C6H6N2O)(H2O)2], contains two 4-(dimethylamino)benzoate (DMAB) ligands, one isonicotinamide (INA) ligand and two water molecules; one of the DMAB ions acts as a bidentate ligand while the other and INA are monodentate ligands. The four O atoms in the equatorial plane around the Zn atom form a distorted square-planar arrangement, while the distorted octahedral coordination is completed by the N atom of the INA ligand and the O atom of the water molecule in the axial positions. Intramolecular C—H...O hydrogen bonding results in the formation of a six-membered ring adopting an envelope conformation. The dihedral angle between the carboxyl groups and the adjacent benzene rings are 4.87 (16) and 2.2 (2)°, while the two benzene rings are oriented at a dihedral angle of 65.13 (8)°. The dihedral angle between the benzene and pyridine rings are 11.47 (7) and 74.83 (8)°, respectively. In the crystal structure, intermolecular O—H...O, O—H...N and N—H...O hydrogen bonds link the molecules into a supramolecular structure. π–π contacts between the pyridine and benzene rings and between the benzene rings [centroid–centroid distances = 3.695 (1) and 3.841 (1) Å, respectively] further stabilize the structure. Weak intermolecular C—H...π interactions are also present.

scholarly journals The synthesis and characterization of nickel(II) and copper(II) complexes with the polydentate dialkyl dithiocarbamic acid ligand 3-dithiocarboxy-3-aza-5-aminopentanoate

2002 ◽  
Vol 67 (2) ◽  
pp. 115-122 ◽  
Author(s):  
Srecko Trifunovic ◽  
Zorica Markovic ◽  
Dusan Sladic ◽  
Katarina Andjelkovic ◽  
Tibor Sabo ◽  
...  
Keyword(s):  
Magnetic Susceptibility ◽  
Elemental Analysis ◽  
Electronic Spectra ◽  
Direct Synthesis ◽  
Synthesis And Characterization ◽  
Acid Ligand ◽  
Square Planar ◽  
Dithiocarbamic Acid ◽  
Square Planar Complexes

Square planar complexes of Ni(II) and Cu(II) with potassium 3-dithiocarboxy 3-aza-5-aminopentanoate have been prepared by direct synthesis. The obtained neutral complexes were characterized by elemental analysis, magnetic susceptibility measurements, infrared and electronic spectra. The thermal behaviour of both the Ni(II) and Cu(II) complexes, and the ligand itself was investigated by DSC and TG.

Chlorine nuclear quadrupole resonance in some chloro complexes of divalent copper

1971 ◽  
Vol 24 (10) ◽  
pp. 1993 ◽  
Author(s):  
DE Scaife
Keyword(s):  
Nuclear Quadrupole Resonance ◽  
Covalent Bonding ◽  
Divalent Copper ◽  
Chloro Complexes ◽  
35Cl Nucleus ◽  
Square Planar ◽  
Bonding Interaction ◽  
Quadrupole Resonance ◽  
Square Planar Complexes ◽  
Nuclear Quadrupole

Nuclear quadrupole resonance for the 35Cl nucleus has been observed in some chloro complexes of divalent copper. Square-planar complexes each show two resonance lines, with the following frequencies (at 77�K): (CH3NH3)2CuCl4, 10.780, 12.157 MHz; (C2H5NH3)2CuCl4, 10.817, 12.074 MHz; (enH2)CuCl4, 10.271, 11.901 MHz; and (C3H7NH3)2CuCl4 at 223�K, 11.290 and 11.781 MHz. NH4CuCl3, containing dimeric Cu2Cl62- units, has resonances, at 77�K, at 11.907, 11.993, and 12.448 MHz. The trigonal pyramidal anion in Co(NH3)6CuCl5 has two resonances at 9.642 and 10.352 MHz at 77�K. ��� These results are compared with previous results for copper chloro complexes, and the implications of covalent bonding are discussed. In particular, it is suggested that the long-bond interaction between units in square-planar complexes amounts to 7-16% of the bonding interaction within the units.

Extended X-ray absorption fine structure and multiple-scattering simulation of nickel dithiolene complexes Ni[S2C2(CF3)2]2n(n= −2, −1, 0) and an olefin adduct Ni[S2C2(CF3)2]2(1-hexene)

2015 ◽  
Vol 22 (1) ◽  
pp. 124-129 ◽  
Author(s):  
Weiwei Gu ◽  
Hongxin Wang ◽  
Kun Wang
Keyword(s):  
Fine Structure ◽  
Multiple Scattering ◽  
Edge Structure ◽  
X Ray ◽  
Absorption Fine ◽  
Square Planar ◽  
Square Planar Complexes ◽  
Uv Visible ◽  
Edge Features ◽  
X Ray Absorption

A series of Ni dithiolene complexes Ni[S2C2(CF3)]2n(n= −2, −1, 0) (1,2,3) and a 1-hexene adduct Ni[S2C2(CF3)2]2(C6H12) (4) have been examined by NiK-edge X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine-structure (EXAFS) spectroscopies. Ni XANES for1–3reveals clear pre-edge features and approximately +0.7 eV shift in the NiK-edge position for `one-electron' oxidation. EXAFS simulation shows that the Ni—S bond distances for1,2and3(2.11–2.16 Å) are within the typical values for square planar complexes and decrease by ∼0.022 Å for each `one-electron' oxidation. The changes in NiK-edge energy positions and Ni—S distances are consistent with the `non-innocent' character of the dithiolene ligand. The Ni—C interactions at ∼3.0 Å are analyzed and the multiple-scattering parameters are also determined, leading to a better simulation for the overall EXAFS spectra. The 1-hexene adduct4presents no pre-edge feature, and its NiK-edge position shifts by −0.8 eV in comparison with its starting dithiolene complex3. Consistently, EXAFS also showed that the Ni—S distances in4elongate by ∼0.046 Å in comparison with3. The evidence confirms that the neutral complex is `reduced' upon addition of olefin, presumably by olefin donating the π-electron density to the LUMO of3as suggested by UV/visible spectroscopy in the literature.

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