o-Lithiothiophenol equivalents. Generation, reactions and applications in synthesis of hindered thiolate ligands

Block, Eric; Eswarakrishnan, Venkatachalam; Gernon, Michael; Ofori-Okai, Gabriel; Saha, Chantu Ranjan; Tang, Kaluo; Zubieta, Jon

doi:10.1021/ja00184a039

Cited by 147 publications

(74 citation statements)

References 2 publications

(7 reference statements)

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“…[23] Ortho-formylation of 5 a to yield aldehyde 6 a was achieved following modified literature procedures. [24][25][26] The use of 1-formylpiperidine as formylating agent in place of the previously reported N,N-dimethylform-A C H T U N G T R E N N U N G amide increased the yield from about 55 % to about 80 %.…”

Section: Resultsmentioning

confidence: 87%

Molecular and Electronic Structures of One‐Electron Oxidized Ni^II–(Dithiosalicylidenediamine) Complexes: Ni^III–Thiolate versus Ni^II–Thiyl Radical States

Stenson

Board

Marín-Becerra

et al. 2008

Chemistry A European J

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The dithiosalicylidenediamine Ni II complexes [Ni(L)] (R=tBu, R'=CH2C(CH3)2CH2 1, R'=C6H4 2; R=H, R'=CH2C(CH3)2CH2 3, R'=C6H4 4) have been prepared by transmetallation of the tetrahedral complexes [Zn(L)] (R=tBu, R'=CH2C(CH3)2CH2 7, R'=C6H4 8; R=H, R'=CH2C(CH3)2CH2 9, R'=C6H4 10) formed by condensation of 2,4-di-R-thiosalicylaldehyde with diamines H2N-R'-NH2 in the presence of Zn II salts. The diamagnetic mononuclear complexes [Ni(L)] show a distorted square-planar N2S2 coordination environment and have been characterized by 1H- and 13C NMR and UV/Vis spectroscopies and by single-crystal X-ray crystallography. Cyclic voltammetry and coulombic measurements have established that complexes 1 and 2, incorporating tBu functionalities on the thiophenolate ligands, undergo reversible one-electron oxidation processes, whereas the analogous redox processes for complexes 3 and 4 are not reversible. The one-electron oxidized species, 1+ and 2+, can be generated quantitatively either electrochemically or chemically with 70 % HClO4. EPR and UV/Vis spectroscopic studies and supporting DFT calculations suggest that the SOMOs of 1+ and 2+ possess thiyl radical character, whereas those of 1(py)2 + and 2(py)2 + possess formal Ni III centers. Species 2+ dimerizes at low temperature, and an X-ray crystallographic determination of the dimer [(2)2](ClO4)2.2 CH2Cl2 confirms that this dimerization involves the formation of a S-S bond (S...S=2.202(5) A).

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Section: Resultsmentioning

confidence: 87%

Molecular and Electronic Structures of One‐Electron Oxidized Ni^II–(Dithiosalicylidenediamine) Complexes: Ni^III–Thiolate versus Ni^II–Thiyl Radical States

Stenson

Board

Marín-Becerra

et al. 2008

Chemistry A European J

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“…The yield of 11 was low due to the selectivity of ortho lithiation of 2-naphthalenethiol. [12] ortho Lithiation occurred in both the C 1 and C 3 positions. Another isomer of 11, which was fused at the C 1 -C 2 position, was also generated in a little amount.…”

Section: Synthesis Of Naphtho[12345]tetrathiaselenepinsmentioning

confidence: 96%

“…However, almost pure 11 was obtained after recrystallization. Compound 11 was also treated with S 8 /NH 3 according to the conditions of Scheme 1, and naphtho [2,3- (12) was isolated in 70 % yield as a pale yellow powder. Here, neither the five-membered ring nor any other isomer was isolated.…”

Section: Synthesis Of Naphtho[12345]tetrathiaselenepinsmentioning

confidence: 99%

“…[11] Lithiation of 1-naphthalenethiol has already been performed. [12] Selenation of a lithiated mixture of 1-naphthalenethiol and successive air oxidation afforded the well-known naphtho [1,8-cd]-1,2-selenathiole (13) in 30 % yield along with some insoluble oligomers (Scheme 4). [13] Protection of naphthalenedichalcogenols in bulk under neutral conditions with dimethyltin(IV) dichloride gave compound 14 in only 16 % yield.…”

Section: Synthesis Of Naphtho[12345]tetrathiaselenepinsmentioning

confidence: 99%

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Selenium‐Containing Tetrachalcogenins and Pentachalcogenepins Fused to Aromatic Systems

et al. 2007

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Various ring-sized cyclic polychalcogenides fused to aromatic systems were synthesized, and the structures were sufficiently characterized. Stabilities of the rings were examined in terms of the existence of selenium atoms. Benzopolychalcogenides are unstable molecules. However, benzo[1,2,3,4,5]-tetrathiaselenepins with an isopropyl group or two methoxy groups on the ring were found to be stable. Similarly, the novel benzo[2,3,4,1,5]trithiadiselenepin ring was also stabilized by two methoxy groups. Benzo[1,2,3,4]trithiaselenin and benzo[2,3,1,4]dithiadiselenin were also synthesized by a controlled reaction with S 2 Cl 2 at -78°C. The ring systems were sensitive to air, moisture, light, and polar solvents. Extended π-systems such as naphthalene and phenanthrene showed remarkable thermodynamic stability toward un-

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“…Particularly, phosphanylarenethiol proligands can be obtained [248,249] In a similar way, 2-(trimethylsilyl)benzenethiol can also be used for this kind of syntheses; the silylated derivative can be obtained by reaction between thiophenol, nbutyllithium and TMEDA in cyclohexane in a first step [250], which is followed by the addition of chlorotrimethylsilane (Scheme 13).…”

Section: Scheme 12mentioning

confidence: 99%

The use of sacrificial anodes for the electrochemical synthesis of metallic complexes

Rodríguez

García‐Vázquez

2015

Coordination Chemistry Reviews

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o-Lithiothiophenol equivalents. Generation, reactions and applications in synthesis of hindered thiolate ligands

Cited by 147 publications

References 2 publications

Molecular and Electronic Structures of One‐Electron Oxidized Ni^II–(Dithiosalicylidenediamine) Complexes: Ni^III–Thiolate versus Ni^II–Thiyl Radical States

Molecular and Electronic Structures of One‐Electron Oxidized Ni^II–(Dithiosalicylidenediamine) Complexes: Ni^III–Thiolate versus Ni^II–Thiyl Radical States

Selenium‐Containing Tetrachalcogenins and Pentachalcogenepins Fused to Aromatic Systems

The use of sacrificial anodes for the electrochemical synthesis of metallic complexes

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o-Lithiothiophenol equivalents. Generation, reactions and applications in synthesis of hindered thiolate ligands

Cited by 147 publications

References 2 publications

Molecular and Electronic Structures of One‐Electron Oxidized NiII–(Dithiosalicylidenediamine) Complexes: NiIII–Thiolate versus NiII–Thiyl Radical States

Molecular and Electronic Structures of One‐Electron Oxidized NiII–(Dithiosalicylidenediamine) Complexes: NiIII–Thiolate versus NiII–Thiyl Radical States

Selenium‐Containing Tetrachalcogenins and Pentachalcogenepins Fused to Aromatic Systems

The use of sacrificial anodes for the electrochemical synthesis of metallic complexes

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Product

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Molecular and Electronic Structures of One‐Electron Oxidized Ni^II–(Dithiosalicylidenediamine) Complexes: Ni^III–Thiolate versus Ni^II–Thiyl Radical States

Molecular and Electronic Structures of One‐Electron Oxidized Ni^II–(Dithiosalicylidenediamine) Complexes: Ni^III–Thiolate versus Ni^II–Thiyl Radical States