Synthesis and characterization of [H2NC(S)NP(S)(OiPr)2]− complexes of Co(II), Ni(II), Zn(II) and Cd(II)

Safin, Damir A.; Babashkina, Maria G.; Bolte, Michael; Klein, Axel

doi:10.1016/j.ica.2010.07.048

Cited by 15 publications

(20 citation statements)

References 63 publications

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“…Indeed, the complex units of [NiL I 2 ] exhibit intermolecular N–H ··· S=C hydrogen bonds, which is not the case for the remaining systems [NiL II,IV 2 ] ; the energetically slightly disfavoured 1,5‐ S , S′ isomer presumably has a better tendency to crystallize. The same probably holds too for the recently reported derivatives [Ni{RC(S)NHP(S)(O i Pr) 2 } 2 ] (R = H 2 N, MeNH, PhNH),6b,8b,10a which all have been found in the 1,5‐ S , S′ isomeric form in their crystal structures. It should be noted that the recently reported complexes [Ni{RC(S)NHP(S)(O i Pr) 2 } 2 ] (R = t BuNH, AdNH) have also been found to be 1,5‐ S , S′ ‐coordinated, and no inter‐ or intramolecular hydrogen bonds have been found in the solid state 4d,10b.…”

Section: Resultssupporting

confidence: 67%

“…From the rather small extinction coefficients ( ϵ = 103–257 M –1 cm –1 ) compared with those of the bands in the UV region, the two long‐wavelength bands are assigned to ligand‐field (d–d) transitions. For a square‐planar 3d 8 system three bands [ 1 A 1g → 1 B 1g (d

_{italicx^{2} – italicy^{2}}

→d xy ), 1 A 1g → 1 B 3g (d xz →d xy ) and 1 A 1g → 1 B 1g (d

_{italicz^{2}}

→d xy ); assuming the orbital ordering: d xy > d

_{italicx^{2} – italicy^{2}}

> d yz > d xz > d

_{italicz^{2}}

] are expected 3a,6b,10a,13. However, comparison with spectra of related complexes suggest that the third band is hidden under the tail of the intense intraligand bands.…”

Section: Resultsmentioning

confidence: 99%

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Crucial Influence of the Intramolecular Hydrogen Bond on the Coordination Mode of RC(S)NHP(S)(OiPr)₂ in Homoleptic Complexes with Ni^II

et al. 2012

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Reaction of the deprotonated N-thiophosphorylated thioureas RC(S)NHP(S)(OiPr) 2 [R = EtNH (HL I ), iPrNH (HL II ), Et 2 N (HL III ), 2,5-Me 2 C 6 H 3 NH (HL IV ), 4-Me 2 NC 6 H 4 NH (HL V )] with Ni II leads to complexes of the formula [NiL I-V 2 ]. The molecular structures of the complexes in the solid were elucidated by single-crystal X-ray diffraction analysis. In the complexes, the metal atom is found to be in a square-planar trans-N 2 S 2 ([NiL II,IV 2 ]) environment formed by the C=S sulfur atoms and the P-N nitrogen atoms, or in a square-planar trans-S 2 SЈ 2 ([NiL I,III 2 ]) environment formed by the C=S and P=S sulfur atoms of two deprotonated ligands. Reaction of deprotonated N-thiophosphorylated thiourea HL V with NiCl 2 leads to violet [Ni(L-1,3-N,S) 2 ] or dark violet [Ni(L-1,5-S,SЈ) 2 ]· (CH 3 ) 2 C=O crystals that were isolated by recrystallization from a mixture of CH 2 Cl 2 or acetone, respectively, and nhexane. DFT calculations confirmed that the [Ni(L I,II,IV,V -[a] Institute of Condensed Matter and Nanosciences, 545 N,S) 2 ] conformers are more stable (by 5-7 kcal/mol) than [Ni-(L I,II,IV,V -S,SЈ) 2 ], whereas [Ni(L III -N,S) 2 ] is less stable (by 7-9 kcal/mol) than [Ni(L III -S,SЈ) 2 ]. The main reason for higher stability of the 1,3-N,S versus 1,5-S,SЈ isomers is the formation of intramolecular N-H···S=P hydrogen bonds. The same hydrogen bonds are impossible in complex [NiL III 2 ]. In solution, complex [NiL III 2 ] has revealed an exclusively 1,5-S,SЈ coordination, whereas compounds [NiL I,II,IV,V 2 ] reveal at least two isomers in the 1 H and 31 P{ 1 H} NMR spectra. The major species is assigned to the 1,3-N,S-coordinated isomer, and the minor signals are assigned to the 1,5-S,SЈ isomer, which was confirmed by UV/Vis spectroscopic results. The electrochemical measurements reveal reversible one-electron reduction and irreversible oxidations both assigned to ligand-centred processes. Ligand-based oxidation processes agree well with TD-DFT results.Eur. J. Inorg. Chem. 2013, 545-555 [NiL I,II,IV,V 2 ] contain the characteristic band for the alk-ylNH or arylNH group at 3138-3369 cm -1 . Furthermore, the spectrum of the acetone solvate [Ni(L V -1,5-S,SЈ) 2 ]· (CH 3 ) 2 C=O contains an intense band at 1702 cm -1 corresponding to the C=O group.The 31 P{ 1 H} NMR spectra of [NiL I,II,IV,V 2 ] in CDCl 3 are rather complicated and contain two signals at δ = 50.7-50.9 and 53.6-54.3 ppm for [NiL I,IV 2 ] and four signals at δ = 50.7-51.0, 53.5-54.4, 55.0-55.3 and 58.0-58.4 ppm for [NiL II,V 2 ]. The same was previously observed in the spectra of the complexes [Ni{RNHC(S)NP(S)(OiPr) 2 } 2 ] (R = tBu, Ad, Ph, 2-MeC 6 H 4 , 2,6-Me 2 C 6 H 3 , 2,4,6-Me 3 C 6 H 2 ) in CD 2 Cl 2 or CDCl 3 . [4d,8,10] The high-field signal corresponds to the trans-1,5-S,SЈ coordination, whereas the second signal is typical for the trans-1,3-N,S coordination of the deprotonated ligands. [4d,8,10] In view of the similar intensity and line width of the two low-field signals in the spectra of [NiL II,V 2 ], they are diastereot...

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Section: Resultssupporting

confidence: 67%

_{italicx^{2} – italicy^{2}}

→d xy ), 1 A 1g → 1 B 3g (d xz →d xy ) and 1 A 1g → 1 B 1g (d

_{italicz^{2}}

→d xy ); assuming the orbital ordering: d xy > d

_{italicx^{2} – italicy^{2}}

> d yz > d xz > d

_{italicz^{2}}

] are expected 3a,6b,10a,13. However, comparison with spectra of related complexes suggest that the third band is hidden under the tail of the intense intraligand bands.…”

Section: Resultsmentioning

confidence: 99%

Crucial Influence of the Intramolecular Hydrogen Bond on the Coordination Mode of RC(S)NHP(S)(OiPr)₂ in Homoleptic Complexes with Ni^II

et al. 2012

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“…They can be assigned to the ligand field (d‐d) transitions. For a square planar d 8 ‐system the classical notation of the three allowed transitions is 1 A 1g → 1 B 1g (dx 2 –y 2 →dxy), 1 A 1g → 1 B 3g (dxz→dxy), and 1 A 1g → 1 B 1g (dz 2 →dxy), assuming the orbital ordering dxy>dx 2 –y 2 >dyz>dxz>dz 2 [57,58] . However this ordering is in line with the z axis bisecting the complex in the coordination plane as the main symmetry axis and the x axis being perpendicular to this plane.…”

Section: Resultsmentioning

confidence: 99%

Dinuclear Nickel(II) and Copper(II) Complexes of 8‐Quinoline‐1H‐pyrazole‐3‐carboxamide: Crystal Structure, Magnetic Properties, and DFT Calculations

et al. 2021

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Homoleptic dinuclear complexes [M2(qpyzc)2] (M=Cu (1) or Ni (2) were obtained from the readily synthesised trischelate pyrazole‐based qpyzc ligand (H2qpyzc=8‐quinoline‐1H‐pyrazole‐3‐carboxamide). Their crystal and molecular structures, magnetic properties, and UV‐vis spectra were reported alongside with DFT and TD‐DFT calculations. Trigonality index τ’4 values of 0.25 and 0.21 for the Cu and Ni centres, respectively reveal a marked distortion from square planar geometry. The two metal coordination planes within a complex are tilted towards each other with 40.2(1)° for Cu(II) and 34.5(2)° for Ni(II). The central six‐membered M2N4 metallocycle is almost planar and the two anionic pyrazolate rings are tilted towards each other by 37.4(1)° (1) and 38.5(2)° (2), respectively. Regardless of this peculiar bonding situation magnetic measurements on 1 are in line with medium‐sized antiferromagnetic coupling with a coupling constant of J=−100 cm−1, an isotropic g value of 2.11 and an S=0 ground state. Complex 2 seems to be diamagnetic. DFT calculations gave an excellent agreement between calculated and experimental metrics of the complexes and supported the prevalence of the singlet ground state for 1. TD‐DFT calculated UV‐vis absorption spectra agree well with observed absorptions and the red colour of both compounds.

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“…In addition, they have several donor atoms able to coordinate metal ions, thereby they can display a variety of coordination modes in the complexes with transition metals, depending on the intramolecular interactions and the corresponding preferable conformations. As it was shown in a series of publications [17][18][19][20][21][22][23][24][25], the most abundant coordination mode of thiophosphorylated thioureas is 1,5-S,S metal coordination with the formation of the six-membered metal containing cyclic fragments, while the 1,3-N,S mode is rare [12,20,24,26,27].…”

Section: Resultsmentioning

confidence: 99%

“…97-99 • C; IR (KBr): ν (cm −1 ) 3234 (NH), 1541, 1487 (NCS), 1017 (C-O-P), 614 (P=S); 1 H NMR (400 MHz, CDCl 3 ): δ (ppm) 1. 25 Single crystals, suitable for X-ray diffraction analysis, were obtained by slow evaporation of the mother liquor after precipitate filtration.…”

Section: Syntheses (±)-1-(1234-tetrahydronaphthalen-1-yl)-3-(oo-dmentioning

confidence: 99%

Chirality Control in Crystalline Ni(II) Complexes of Thiophosphorylated Thioureas

et al. 2019

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Chirality control over the formation of Ni(II) complexes with chiral thiophosphorylated thioureas was achieved via breaking the symmetry of nickel coordination geometry by the introduction of the pyridine ligand, while centrosymmetric meso-complexes are formed from racemic ligands in case of square-planar nickel coordination. Centrosymmetric heterochiral arrangement is observed in crystals of ligands themselves through N–H⋅⋅⋅S hydrogen bonds in intermolecular dimers. Molecular homochirality in tetragonal pyramidal complexes is further transferred to supramolecular homochiral arrangement via key–lock steric interactions.

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Synthesis and characterization of [H2NC(S)NP(S)(OiPr)2]− complexes of Co(II), Ni(II), Zn(II) and Cd(II)

Cited by 15 publications

References 63 publications

Crucial Influence of the Intramolecular Hydrogen Bond on the Coordination Mode of RC(S)NHP(S)(OiPr)₂ in Homoleptic Complexes with Ni^II

Crucial Influence of the Intramolecular Hydrogen Bond on the Coordination Mode of RC(S)NHP(S)(OiPr)₂ in Homoleptic Complexes with Ni^II

Dinuclear Nickel(II) and Copper(II) Complexes of 8‐Quinoline‐1H‐pyrazole‐3‐carboxamide: Crystal Structure, Magnetic Properties, and DFT Calculations

Chirality Control in Crystalline Ni(II) Complexes of Thiophosphorylated Thioureas

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Synthesis and characterization of [H2NC(S)NP(S)(OiPr)2]− complexes of Co(II), Ni(II), Zn(II) and Cd(II)

Cited by 15 publications

References 63 publications

Crucial Influence of the Intramolecular Hydrogen Bond on the Coordination Mode of RC(S)NHP(S)(OiPr)2 in Homoleptic Complexes with NiII

Crucial Influence of the Intramolecular Hydrogen Bond on the Coordination Mode of RC(S)NHP(S)(OiPr)2 in Homoleptic Complexes with NiII

Dinuclear Nickel(II) and Copper(II) Complexes of 8‐Quinoline‐1H‐pyrazole‐3‐carboxamide: Crystal Structure, Magnetic Properties, and DFT Calculations

Chirality Control in Crystalline Ni(II) Complexes of Thiophosphorylated Thioureas

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Crucial Influence of the Intramolecular Hydrogen Bond on the Coordination Mode of RC(S)NHP(S)(OiPr)₂ in Homoleptic Complexes with Ni^II

Crucial Influence of the Intramolecular Hydrogen Bond on the Coordination Mode of RC(S)NHP(S)(OiPr)₂ in Homoleptic Complexes with Ni^II