Intramolecular hydrogen bond controlled coordination of N-thiophosphorylated thiourea 2,6-Me2C6H3NHC(S)NHP(S)(OiPr)2 with Ni(II)

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

doi:10.1016/j.inoche.2009.05.030

Cited by 26 publications

(23 citation statements)

References 11 publications

(11 reference statements)

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“…These signals are low-field shifted relative to that in the spectra of HL I-V and H 2 L VI,VII [1,5,12,13]. The signal of the phosphorus atom of PPh 4 + in the spectra was found at 22.4-24.1 ppm.…”

Section: Resultsmentioning

confidence: 77%

“…The crystal structure modification of PhC(S)NHP(S)(O-i-Pr) 2 (HQ) is also reported. were prepared by reaction of the corresponding amine with (i-PrO) 2 P(S)NCS as described previously [5,12,13] I . In the spectra of all obtained salts, there are intense absorption bands of the conjugated SCN group in the area 1520-1564 cm −1 .…”

Section: Methodsmentioning

confidence: 99%

“…N-Thiophosphorylated thioureas HL I-V were syhthesized as previously described [5,12,13]. Bis-thioureas H 2 L V,VI were syhthesized as previously described [5].…”

Section: Methodsmentioning

confidence: 99%

“…Results of our structure solution and refinement are collected in Table 1 together with those of polymorph B. A representative view of the C2/c structure is shown in (1) O(1) 115.22 (13) …”

Section: And [Phc(s)np(s)(oipr) 2 ]mentioning

confidence: 99%

“…115.30 (13) 114.96(7) O(1) P (1) O(2) 103.81 (12) 104.94(6) O(3) P (1) N(1) 107.52 (13) 107.05(7) O(1) P (1) N(1) 105.08 (13) 105.61(7) O(2) P (1) N(1) 109.37 (12) 109.09(7) C(1) N (1) P(1) 126.7 (2) …”

Section: 73(7) O(3) P(1) O(2)mentioning

confidence: 99%

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Tetraphenylphosphonium salts of N‐thiophosphorylated thiobenzamide, mono‐thioureas or bis‐thioureas

Safin¹,

Babashkina²,

Bolte³

et al. 2010

Heteroatom Chemistry

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Reaction of the sodium salts of RC(S) NHP(S)(O‐i‐Pr)2 (R = Ph, HLI; PhNH, HLII; 2‐MeC6H4NH, HLIII; 2,6‐Me2C6H3NH, HLIV; 2,4,6‐Me3C6H2NH, HLV) or Z[NHC(S)NHP(S)(O‐i‐Pr)2]2 (Z = o‐C6H4, H2LVI; 1,2‐CH2CH2, H2LVII) with PPh4Br in 96% aqueous EtOH leads to the compounds of formulae PPh4LI–V and (PPh4)2LVI,VII. Compounds obtained were investigated by 1H and 31P{1H} NMR spectroscopy, ES mass spectrometry, and microanalysis. Recrystallization of PPh4LI from an aqueous EtOH solution (1:1, v/v) leads to the formation of PhC(S)NHP(O)(O‐i‐Pr)2 (HQ). The crystal structure of HQ reveals to be a polymorph to the previously reported structure. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:343–350, 2010; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20607

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Section: Resultsmentioning

confidence: 77%

Section: Methodsmentioning

confidence: 99%

“…N-Thiophosphorylated thioureas HL I-V were syhthesized as previously described [5,12,13]. Bis-thioureas H 2 L V,VI were syhthesized as previously described [5].…”

Section: Methodsmentioning

confidence: 99%

“…Results of our structure solution and refinement are collected in Table 1 together with those of polymorph B. A representative view of the C2/c structure is shown in (1) O(1) 115.22 (13) …”

Section: And [Phc(s)np(s)(oipr) 2 ]mentioning

confidence: 99%

Section: 73(7) O(3) P(1) O(2)mentioning

confidence: 99%

See 3 more Smart Citations

Tetraphenylphosphonium salts of N‐thiophosphorylated thiobenzamide, mono‐thioureas or bis‐thioureas

Safin¹,

Babashkina²,

Bolte³

et al. 2010

Heteroatom Chemistry

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Influence of the Homopolar Dihydrogen Bonding CH⋅⋅⋅HC on Coordination Geometry: Experimental and Theoretical Studies

Safin

Babashkina

Robeyns

et al. 2015

Chemistry A European J

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The reaction of the N-thiophosphorylated thiourea (HOCH2 )(Me)2 CNHC(S)NHP(S)(OiPr)2 (HL), deprotonated by the thiophosphorylamide group, with NiCl2 leads to green needles of the pseudotetrahedral complex [Ni(L-1,5-S,S')2 ]⋅0.5 (n-C6 H14 ) or pale green blocks of the trans square-planar complex trans-[Ni(L-1,5-S,S')2 ]. The former complex is stabilized by homopolar dihydrogen C-H⋅⋅⋅H-C interactions formed by n-hexane solvent molecules with the [Ni(L-1,5-S,S')2 ] unit. Furthermore, the dispersion-dominated C-H⋅⋅⋅ H-C interactions are, together with other noncovalent interactions (C-H⋅⋅⋅N, C-H⋅⋅⋅Ni, C-H⋅⋅⋅S), responsible for pseudotetrahedral coordination around the Ni(II) center in [Ni(L-1,5-S,S')2 ]⋅0.5 (n-C6 H14 ).

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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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Intramolecular hydrogen bond controlled coordination of N-thiophosphorylated thiourea 2,6-Me2C6H3NHC(S)NHP(S)(OiPr)2 with Ni(II)

Cited by 26 publications

References 11 publications

Tetraphenylphosphonium salts of N‐thiophosphorylated thiobenzamide, mono‐thioureas or bis‐thioureas

Tetraphenylphosphonium salts of N‐thiophosphorylated thiobenzamide, mono‐thioureas or bis‐thioureas

Influence of the Homopolar Dihydrogen Bonding CH⋅⋅⋅HC on Coordination Geometry: Experimental and Theoretical Studies

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

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Intramolecular hydrogen bond controlled coordination of N-thiophosphorylated thiourea 2,6-Me2C6H3NHC(S)NHP(S)(OiPr)2 with Ni(II)

Cited by 26 publications

References 11 publications

Tetraphenylphosphonium salts of N‐thiophosphorylated thiobenzamide, mono‐thioureas or bis‐thioureas

Tetraphenylphosphonium salts of N‐thiophosphorylated thiobenzamide, mono‐thioureas or bis‐thioureas

Influence of the Homopolar Dihydrogen Bonding CH⋅⋅⋅HC on Coordination Geometry: Experimental and Theoretical Studies

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

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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