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Trans influence of triphenylphosphines and pseudohalogens on Ni-S bonds: Synthesis, spectral and single crystal X-ray structural studies on NiS2PN and NiS2PC chromophores

100%
Ramalingam K., Thiruneelakandan R., Bocelli G., Righi L.
Open Chemistry
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2012
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vol. 10
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issue 4
1199-1207
EN
Trans influence of triphenylphosphines and pseudohalogens on Ni-S bonds of NiS2PN and NiS2PC chromophores has been investigated by synthesizing and characterizing them. The complexes show the characteristic thioureide IR band at ∼ 1530 cm−1. Electronic spectrum of the cyanide analogue shows a strong blue shift relative to others. X-ray structures of [Ni(pipdtc)(4-MP)(NCS)] (1), [Ni(pipdtc)(PPh3)(NCS)] (2) and [Ni(pipdtc)(PPh3)(CN)] (3) (pipdtc = piperidinecarbodithioate anion, 4-MP = tri(4-methylphenyl)phopshine) are reported. Ni-S bond distance trans to 4-MP(1) is longer than the distances in (2) and (3) and Ni-S bond distances trans to Ni-NCS/CN decrease as follows: (3) > (2) > (1). Particularly, 4-MP shows a highly significant trans influence than triphenylphosphine on Ni-S bond. Similarly, CN− exerts a marginally significant trans influence compared to NCS-. Thioureide C-N distances are relatively very short due to the drift of electron density towards the metal. The Ni-N-C angle (163.5(2)°) observed in (2) indicates deviation from linearity to a larger extent compared to that in (1) (176.3(3)°) due to the steric effect of the 4-methyl group. The reduction potentials (CV) for the mixed ligand complexes are much less compared to that of the parent NiS4 chromophore due to the π-acidic phosphines. [...]
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Hydrogen-bonding network in the organic salts of 4-nitrobenzoic acid

76%
Chumakov Y., Simonov Y., Grozav M., Crisan M., Bocelli G., Yakovenko A., Lyubetsky D.
Open Chemistry
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2006
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vol. 4
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issue 3
458-475
EN
The crystal structures of six novel salts of 4-nitrobenzoic acid - namely, 2-hydroxyethylammonium 4-nitrobenzoate (I), 2-hydroxypropylammonium 4-nitrobenzoate (II), 1-(hydroxymethyl)propylammonium 4-nitrobenzoate (III), 3-hydroxypropylammonium 4-nitrobenzoate (IV), bis-(2-hydroxyethylammonium) 4-nitrobenzoate (V), morpholinium 4-nitrobenzoate (VI) - containing the same anion but different cations have been studied. The ionic forms of I-VI serve as building blocks of the supramolecular architecture, and in crystals they are held together via ionic N-H···O and O-H···O hydrogen bonds. In the crystal packing the building blocks of I-III are self-assembled via N-H...O, O-H···O and C-H...O hydrogen bonds to form the chains which are further consolidated into two-dimensional layers by the same type of interactions. In IV-VI the chain-like structures have been generated by building blocks.
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