Five new complexes based on 1-phenyl-1 H -tetrazole-5-thiol: Synthesis, structural characterization and properties

Song, Jiangfeng; Wang, Jun; Li, Sizhe; Li, Yang; Zhou, Rui-Sha

doi:10.1016/j.molstruc.2016.09.053

Cited by 26 publications

(8 citation statements)

References 39 publications

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“…Therefore, besides characterization of 1 (ClO 4 ) 2 by molecular structure determination, elemental analysis, and mass spectrometry, 1 was characterized further by IR spectroscopy and X-ray photoelectron spectroscopy (XPS). Compound 1 (ClO 4 ) 2 showed ν S–H stretching at 2516 cm –1 for the bridging −SH functionality (Figure S8), which is in accord with the ν S–H values of transition metal–hydrosulfide complexes reported in the literature. ,,,− Due to the presence of ClO 4 – as the counteranion in 1 (ClO 4 ) 2 , the presence of −SH (as opposed to chloride) was further confirmed by the X-ray photoelectron spectroscopy (Figure ) of 1 (BF 4 ) 2 which was synthesized following a procedure analogous to that for 1 (ClO 4 ) 2 (see Figures S8 and S9 for the IR and mass spectrum, respectively). The characteristic peak for sulfur ,, in 1 (BF 4 ) 2 was observed at 161.20 eV (Figure b) while the characteristic peak of chloride ,, at ∼197 eV (Cl 2p 3/2 ) and at ∼198 eV (Cl 2p 1/2 ) was found to be absent (Figure c).…”

Section: Resultssupporting

confidence: 84%

Thiolate Coordination vs C–S Bond Cleavage of Thiolates in Dinickel(II) Complexes

2021

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A detailed study for the synthesis of dinickel(II)–thiolate and dinickel(II)–hydrosulfide complexes and the complete characterization of the relevant intermediates involved in the C–S bond cleavage of thiolates are presented. Hydrated Ni(II) salts mediate the hydrolytic C–S bond cleavage of thiolates (NaSR/RSH; R = Me, Et, n Bu, t Bu), albeit inefficiently, to yield a mixture of a dinickel(II)–hydrosulfide complex, [Ni2(BPMP)(μ-SH)(DMF)2]2+ (1), and the corresponding dinickel(II)–thiolate complexes, such as [Ni2(BPMP)(μ-SEt)(ClO4)]1+ (2) (HBPMP is 2,6-bis[[bis(2-pyridylmethyl)amino]methyl]-4-methylphenol). A systematic study for the reactivity of thiolates with Ni(II) was therefore pursued which finally yielded 1 as a pure product which has been characterized in comparison with the dinickel(II)–dichloride complex, [Ni2(BPMP)(Cl)2(MeOH)2]1+ (3). While the reaction of thiolates with anhydrous Ni(OTf)2 in dry conditions could only yield [Ni2(BPMP)(OTf)2]1+ (5) instead of the expected dinickel(II)–thiolate compound, the C–S bond cleavage could be suppressed by the use of a chelating thiol, such as PhCOSH, to yield [Ni2(BPMP)(SCOPh)2]1+ (6). Finally, with the suitable choice of a monodentate thiol, a dinickel(II)–monothiolate complex, [Ni2(BPMP)(SPh)(DMF)(MeOH)(H2O)]2+ (7), was isolated as a pure product within 1 h of reaction, which after a longer time of reaction yielded 1 and PhOH. Complex 7 may thus be regarded as the intermediate that precedes the C–S bond cleavage and is generated by the reaction of a thiolate with an initially formed dinickel(II)–solvento complex, [Ni2(BPMP)(MeOH)2(H2O)2]3+(4). Selected dinickel(II) complexes were explored further for the scope of substitution reactions, and the results include the isolation of a dinickel(II)–bis(thiolate) complex, [Ni2(BPMP)(μ-SPh)2]1+ (8).

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Section: Resultssupporting

confidence: 84%

Thiolate Coordination vs C–S Bond Cleavage of Thiolates in Dinickel(II) Complexes

2021

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“…Indeed, the structural parameters of 1c and 2d were found to be very similar with those of 1a and 2a , respectively. IR spectroscopic measurements of 1a (BF 4 ) and 2a (BF 4 ) 2 as solid KBr pellets exhibited the ν SH at 2510 and 2493 cm –1 , respectively, which are comparable with the ν SH values reported for metal-hydrosulfide compounds in the literature. ,− No such peak could be observed in the case of the diiron(II)-chloride compounds, 1c (BF 4 ) and 2d (FeCl 4 ) (Figures S10 and S22). Compound 1a (BF 4 ) is orange in color [λ max , nm (ε, M –1 cm –1 ) in MeCN: 288 (1955 ± 10), 416 (835 ± 40), 600 (60 ± 5)] and thus can be easily distinguished from 1c (BF 4 ) (Figure S7), which was isolated as a green crystalline solid [λ max , nm (ε, M –1 cm –1 ) in MeCN: 290 (4090 ± 60), 300 (4095 ± 90), 363 (2130 ± 60), 600 (125 ± 5)].…”

Section: Resultsmentioning

confidence: 98%

Iron(II) Mediated Desulfurization of Organosulfur Substrates Produces Nonheme Diiron(II)-hydrosulfides

2019

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A reaction system involving Fe(BF4)2·6H2O and two dinucleating ligands, HBPMP and HPhBIMP, mediates the desulfurization of aliphatic and aromatic thiols at room temperature. This rare C–S bond cleavage reaction produces two nonheme diiron(II) complexes, [Fe2(BPMP)(SH)2(MeOH)2]1+ (1a) and [Fe2(PhBIMP)(μ-SH)(DMF)]2+ (2a), possibly via an active species similar to [Fe2(PhBIMP)(H2O)2(DMF)2]3+ (2c), while the thiols are converted to the corresponding alcohols/phenols. In the case of thioacetic acid, a bidentate chelating organosulfur substrate, the use of HBPMP produces the corresponding bis-thiocarboxylato bridged complex, [Fe2(BPMP)(CH3COS)2]1+ (1b), instead of 1a. However, the use of HPhBIMP allows the Fe(II) mediated desulfurization of thioacetic acid as well to yield 2a, along with the formation of [Fe2(PhBIMP)(CH3COS)(MeCN)]2+ (2b). This convenient desulfurization reaction has been demonstrated for different substrates in different solvents along with the structural and spectroscopic characterizations of the diiron(II)-hydrosulfide complexes in comparison with two isostructural chloride complexes, [Fe2(BPMP)(Cl)2(MeOH)2]1+ (1c) and [Fe2(PhBIMP)(μ-Cl)(DMF)]2+ (2d). The role of the individual reactants in the desulfurization process has been thoroughly investigated using control reactions, and on the basis of these results and the identification of intermediate species, such as [Fe2(PhBIMP)(S t Bu)(DMF)3]2+ and [Fe2(PhBIMP)(S t Bu)(H2O)(DMF)2]2+, in solution by mass spectrometry, a possible mechanism has been proposed.

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“…The terminal hydrosulfides in 1b showed relatively smaller Co–S distances [2.330(1) and 2.316(1) Å], while the Co–Co distance is comparatively longer (3.344 Å) than that in 1a or 2a . The presence of coordinated −SH groups in 1a , 1b , 2a , and 2c was further confirmed by IR spectroscopy [ν SH = 2493 cm –1 ( 1a ), 2489 cm –1 ( 1b ), 2491 cm –1 ( 2a ), 2514 cm –1 ( 2c )] and 1 H NMR spectroscopy [δ S–H = 44.09 ppm ( 1a ), 44.13 ppm ( 1b ); 36.17 ppm ( 2a ), 36.09 ppm ( 2c )], which are comparable with the data for previously reported metal hydrosulfide complexes. − Analogous chloro complexes [Co 2 (BPMP)(Cl) 2 ](BF 4 ) ( 1d ; CCDC 1857215) and [Co 2 (PhBIMP)(μ 2 -Cl)(DMF)](CoCl 4 ) ( 2e ; CCDC 1857216; Figures S1 and S3) were also synthesized for their use as control compounds for the assignments of 1 H NMR signals and IR stretching frequencies of the coordinated SH groups of 1a , 1b , and 2a and 2c , respectively.…”

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confidence: 77%

Cobalt(II)-Mediated Desulfurization of Thiophenes, Sulfides, and Thiols

et al. 2018

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Desulfurization of organosulfur compounds is a highly important reaction because of its relevance to the hydrodesulfurization (HDS) process of fossil fuels. A reaction system involving Co(BF)·6HO and the dinucleating ligands HBPMP or HPhBIMP has been developed that could desulfurize a large number of thiophenes, sulfides, and thiols to generate the complexes [Co(BPMP)(μ-SH)(MeCN)](BF) (1a), [Co(BPMP)(SH)](BF) (1b), and [Co(PhBIMP)(μ-SH)(X)](BF) [X = DMF (2a), MeCN (2c)], while the substrates are mostly converted to the corresponding alcohols/phenols. This convenient desulfurization process has been demonstrated for 25 substrates in 6 different solvents at room temperature.

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Five new complexes based on 1-phenyl-1 H -tetrazole-5-thiol: Synthesis, structural characterization and properties

Cited by 26 publications

References 39 publications

Thiolate Coordination vs C–S Bond Cleavage of Thiolates in Dinickel(II) Complexes

Thiolate Coordination vs C–S Bond Cleavage of Thiolates in Dinickel(II) Complexes

Iron(II) Mediated Desulfurization of Organosulfur Substrates Produces Nonheme Diiron(II)-hydrosulfides

Cobalt(II)-Mediated Desulfurization of Thiophenes, Sulfides, and Thiols

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