Structural variations of nickel complexes in NiS4 and NiS2PN coordination environments: spectral and single-crystal X-ray structural studies on bis(4-methylpiperidinecarbodithioato-S,S′)nickel(II) and (4-methylpiperidinecarbodithioato-S,S′)(thiocyanato-N)(triphenylphosphine)nickel(II)

Srinivasan, N.; Sathyaselvabala, V.; Kuppulekshmy, K.; Valarmathi, P.; Thirumaran, S.

doi:10.1007/s00706-009-0199-2

Cited by 14 publications

(8 citation statements)

References 21 publications

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“…is 1.8513(16) Å, which is similar to that observed in [Ni(dtc)(NCS)(PPh 3 )] complexes(8,22). Phenyl groups in triphenylphosphine have normal bond parameters.In both the complexes, the thioureide N−C distance [1.326(3) Å in 1 and 1.316(2) Å in 3] indicates that the π-electron density is delocalized over the S 2 CN moiety and that this bond has a strong double-bond character.…”

supporting

confidence: 79%

“…The diversity in applications inherent to nickel(II) complexes with simple and chelating phosphines as catalysts (2)(3)(4) and in the medicinal field (5), combined with their structural novelty, has resulted in the synthesis of a series of compounds with NiS 2 PX (X = halogens or N or C or S) chromophores. Dithiocarbamates have proven to be versatile metal chelates and in particular nickel(II) dithiocarbamates with a planar NiS 4 chromophore are found to show interesting variations in reactivity toward soft Lewis bases such as phosphines (6)(7)(8) and hard bases such as nitrogenous ligands (9)(10)(11). Synthesis, IR, UV-VIS and 1 H NMR spectral studies on [M(dtc) 2 ] (M = Ni, Pt, Zn, Cd; dtc = thqdtc, thiqdtc) have been reported (12,13).…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and spectral studies of Ni(II) heterocyclic dithiocarbamates with S₂PN chromophore: X-ray crystal structures of bis(1,2,3,4-tetrahydroquinolinecarbodithioato- S,S′)nickel(II) and 1,2,3,4-tetrahydroquinolinecarbodithioato-S,S′)(thiocyanato-N)(triphenylphosphine)nickel(II)

Valarmathi

Srinivasan

Thirumaran

2011

Journal of Sulfur Chemistry

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Ni(thqdtc) 2 ] (1), [Ni(thiqdtc) 2 ] (2), [Ni(thqdtc)(NCS)(PPh 3 )] (3) and [Ni(thiqdtc)(NCS)(PPh 3 )](4) (where thqdtc = 1, 2, 3, 4-tetrahydroquinolinedithiocarbamate and thiqdtc = 1, 2, 3, 4-tetrahydroisoquinolinedithiocarbamate) have been characterized by electronic, IR and NMR spectroscopy. The structures of 1 and 3 have been determined by single-crystal X-ray crystallography. The ν C−N (thioureide) is higher for 2 and 4 than for 1 and 3 and the upfield shift of the NCS 2 carbon signal for 4 in comparison to 3 is due to the electron-withdrawing resonance effect of the phenyl ring, thereby decreasing the double-bond character in the tetrahydroquinolinedithiocarbamate. On the other hand, the hyper-conjugative electron withdrawal of the benzyl group present in tetrahydroisoquinolinedithiocarbamate is comparatively less significant than its resonance effect. The N 13 CS 2 carbon signal for 3 is observed at 205.0 ppm with an upfield shift of about 3.7 ppm compared with that found in 1 (208.7 ppm). The observed shielding in 3 indicates the effect of PPh 3 on the mesomeric drift of electron density toward nickel through the thioureide C−N bond. Single-crystal X-ray analysis of 1 and 3 showed that the nickel is in a distorted square planar environment with the NiS 4 and NiS 2 PN chromophores, respectively. A significant asymmetry in the Ni−S bonds is observed in 3 [2.2068(5) and 2.1648(5) Å], whereas in compound 1 the bond distances are similar [2.1041(6) and 2.1968 (5) Å]. The observed difference in Ni−S distance in 3 is attributed to the difference in the trans-influencing properties of PPh 3 and NCS − .

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supporting

confidence: 79%

Section: Introductionmentioning

confidence: 99%

Synthesis and spectral studies of Ni(II) heterocyclic dithiocarbamates with S₂PN chromophore: X-ray crystal structures of bis(1,2,3,4-tetrahydroquinolinecarbodithioato- S,S′)nickel(II) and 1,2,3,4-tetrahydroquinolinecarbodithioato-S,S′)(thiocyanato-N)(triphenylphosphine)nickel(II)

Valarmathi

Srinivasan

Thirumaran

2011

Journal of Sulfur Chemistry

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“…This should be due to the methylene protons of furfuryl and pyrrole methylene protons. 35 This explains the shielding of NCS 2 carbon of heteroleptic complexes. The pyrrole ring proton signals are observed at 6.13, 6.21 and 6.83 ppm, each one corresponding to two protons.…”

Section: Spectroscopymentioning

confidence: 94%

Nickel(ii) dithiocarbamate complexes containing the pyrrole moiety for sensing anions and synthesis of nickel sulfide and nickel oxide nanoparticles

2015

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6) have been prepared and characterized by elemental analysis, IR, 1 H, 13 C NMR, HSQC, HMBC and UV-Vis absorption spectra. For the heteroleptic complexes, the thiocyanide n C-N values were shifted to higher wavenumbers and NCS 2 carbon signals were shifted downfield compared to that of homoleptic complexes, suggesting the increased strength of the thioureide bond due to the presence of p-accepting phosphine. Electronic spectral studies suggest square-planar geometry for the complexes. Complex 5 was also characterized by X-ray diffraction techniques and presents a distorted NiS 2 PN square planar configuration around the Ni atom. Rare C-HÁ Á ÁNi intramolecular short contact interactions were observed in the complex 5.The ability of representative complexes 1 and 2 to sense anions (F À , Cl À , Br À and I À ) was examined by UV-Vis absorption spectra and cyclic voltametric titration studies. These studies show that both the complexes prefer to bind with I À . Complex 2 has been used as a single source precursor for the preparation of nickel sulfide and nickel oxide nanoparticles. The as-prepared nickel sulfide and nickel oxide nanoparticles have been characterized by PXRD, SEM, EDAX, TEM, HRTEM, UV-Vis and Photoluminescence spectroscopy. X-ray diffraction analysis showed the presence of three phases (cubic-NiS 2 , cubic-Ni 3 S 4 and rhombohedral-Ni 3 S 2 ). TEM images of nickel oxide revealed that the particles are spherical in shape with diameter B30 nm.

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“…The observed distortion of the square planar coordination is attributed to the small bite angle of the dithiocarbamate ligand [S1-Ni-S2 = 79.48(3)°]. The Ni-S distances are slightly asymmetric and lie in the expected range for four coordinate dithiocarbamates [5]. In complex 1, the dithiocarbamate ligands are bidentate, giving [20] and Wilton-Ely et al [21].…”

Section: Crystallographic Analysis Of [Ni(dbpdtc) 2 ]mentioning

confidence: 80%

“…Dithiocarbamate ligands display a strong propensity of binding to metal atoms such as nickel [1]. Divalent nickel complexes of dithiocarbamates with different substituents contain the planar diamagnetic NiS 4 chromophore [4,5]. Ni(II) dithiocarbamates are borderline acceptors, and they can react with Lewis bases such as phosphines as well as hard bases such as nitrogenous ligands [6,7].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and spectral studies on NiS4, NiS2PN, NiS2P2 chromophores: Single-crystal X-ray structure of [Ni(dbpdtc)2] (dbpdtc = benzyl(4-(benzylamino)phenyl)dithiocarbamate)

Srinivasan

Valarmathi

Thirumaran

et al. 2010

Transition Met Chem

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Three complexes of a dithiocarbamate ligand (dbpdtc = benzyl(4-(benzylamino)phenyl)dithiocarbamate), namely [Ni(dbpdtc) 2 ] (1), [Ni(dbpdtc)(NCS)(PPh 3 )] (2) and [Ni(dbpdtc)(PPh 3 ) 2 ]ClO 4 (3) have been prepared. The complexes were characterized by IR, electronic spectroscopy and cyclic voltammetry. A single-crystal X-ray structural analysis was carried out for complex 1 and showed that the nickel is in a distorted square planar environment with a NiS 4 chromophore. For the two mixed ligand complexes, the thioureide m C-N values were shifted to higher wavenumbers compared to [Ni(dbpdtc) 2 ], suggesting increased strength of the thioureide bond due to the presence of the p-accepting phosphine. Electronic spectral studies suggest square planar geometries for the complexes. Cyclic voltammetry showed easier reduction of nickel(II) to nickel(I) in the mixed ligand complexes compared to [Ni(dbpdtc) 2 ].

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Structural variations of nickel complexes in NiS4 and NiS2PN coordination environments: spectral and single-crystal X-ray structural studies on bis(4-methylpiperidinecarbodithioato-S,S′)nickel(II) and (4-methylpiperidinecarbodithioato-S,S′)(thiocyanato-N)(triphenylphosphine)nickel(II)

Cited by 14 publications

References 21 publications

Synthesis and spectral studies of Ni(II) heterocyclic dithiocarbamates with S₂PN chromophore: X-ray crystal structures of bis(1,2,3,4-tetrahydroquinolinecarbodithioato- S,S′)nickel(II) and 1,2,3,4-tetrahydroquinolinecarbodithioato-S,S′)(thiocyanato-N)(triphenylphosphine)nickel(II)

Synthesis and spectral studies of Ni(II) heterocyclic dithiocarbamates with S₂PN chromophore: X-ray crystal structures of bis(1,2,3,4-tetrahydroquinolinecarbodithioato- S,S′)nickel(II) and 1,2,3,4-tetrahydroquinolinecarbodithioato-S,S′)(thiocyanato-N)(triphenylphosphine)nickel(II)

Nickel(ii) dithiocarbamate complexes containing the pyrrole moiety for sensing anions and synthesis of nickel sulfide and nickel oxide nanoparticles

Synthesis and spectral studies on NiS4, NiS2PN, NiS2P2 chromophores: Single-crystal X-ray structure of [Ni(dbpdtc)2] (dbpdtc = benzyl(4-(benzylamino)phenyl)dithiocarbamate)

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Structural variations of nickel complexes in NiS4 and NiS2PN coordination environments: spectral and single-crystal X-ray structural studies on bis(4-methylpiperidinecarbodithioato-S,S′)nickel(II) and (4-methylpiperidinecarbodithioato-S,S′)(thiocyanato-N)(triphenylphosphine)nickel(II)

Cited by 14 publications

References 21 publications

Synthesis and spectral studies of Ni(II) heterocyclic dithiocarbamates with S2PN chromophore: X-ray crystal structures of bis(1,2,3,4-tetrahydroquinolinecarbodithioato- S,S′)nickel(II) and 1,2,3,4-tetrahydroquinolinecarbodithioato-S,S′)(thiocyanato-N)(triphenylphosphine)nickel(II)

Synthesis and spectral studies of Ni(II) heterocyclic dithiocarbamates with S2PN chromophore: X-ray crystal structures of bis(1,2,3,4-tetrahydroquinolinecarbodithioato- S,S′)nickel(II) and 1,2,3,4-tetrahydroquinolinecarbodithioato-S,S′)(thiocyanato-N)(triphenylphosphine)nickel(II)

Nickel(ii) dithiocarbamate complexes containing the pyrrole moiety for sensing anions and synthesis of nickel sulfide and nickel oxide nanoparticles

Synthesis and spectral studies on NiS4, NiS2PN, NiS2P2 chromophores: Single-crystal X-ray structure of [Ni(dbpdtc)2] (dbpdtc = benzyl(4-(benzylamino)phenyl)dithiocarbamate)

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Synthesis and spectral studies of Ni(II) heterocyclic dithiocarbamates with S₂PN chromophore: X-ray crystal structures of bis(1,2,3,4-tetrahydroquinolinecarbodithioato- S,S′)nickel(II) and 1,2,3,4-tetrahydroquinolinecarbodithioato-S,S′)(thiocyanato-N)(triphenylphosphine)nickel(II)

Synthesis and spectral studies of Ni(II) heterocyclic dithiocarbamates with S₂PN chromophore: X-ray crystal structures of bis(1,2,3,4-tetrahydroquinolinecarbodithioato- S,S′)nickel(II) and 1,2,3,4-tetrahydroquinolinecarbodithioato-S,S′)(thiocyanato-N)(triphenylphosphine)nickel(II)