Solvent-free one-pot synthesis of thallium complexes of Tp [BH(Pz)3]− (Pz=pyrazolate) and its derivatives

Tsuda, Kazuomi; Miyata, Kengo; Okuno, Takashi; Yoshimura, Masahiro; Tanaka, Shinji; Kitamura, Masato

doi:10.1016/j.tetlet.2008.02.150

Cited by 3 publications

(1 citation statement)

References 25 publications

(8 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The thallium salts of scorpionate ligands are usually obtained by cation exchange, reacting the alkali metal salt with TlNO 3 . In 2008, two new methods were reported by Kitamura et al: i) preparation and isolation of thallium borohydride TlBH 4 and subsequent reaction with pyrazole or indazole derivatives or ii) a solvent‐free one‐pot method using KBH 4 and Tl 2 SO 4 in a 2:1 ratio to yield the thallium hydrotris(pyrazolyl)‐ or hydrotris(indazolyl)borate via an in‐situ cation exchange . Given the toxicity of thallium(I), the latter one‐pot procedure was selected to avoid the isolation of the thallium borohydride reagent.…”

Section: Resultsmentioning

confidence: 99%

Expedient Synthesis of Thioether‐Functionalized Hydrotris(indazolyl)borate as an Anchoring Platform for Rotary Molecular Machines

et al. 2018

View full text Add to dashboard Cite

Major improvements in the synthesis of surface‐mounted rotary molecular machines based on ruthenium(II) complexes are reported. The development of a one‐pot indium(III)‐mediated “N‐deprotection/ester reductive sulfidation” sequence allowed step economy, reproducibility and high efficiency in the synthesis of the thioether‐functionalized tripodal ligand. Switching to the thallium salt of hydrotris(indazolyl)borate and to microwave heating further optimized the preparation of the common intermediate in the modular synthesis of symmetric and dissymmetric molecular motors and gears. The penta(4‐bromophenyl)cyclopentadienyl ruthenium(II) key precursor is now reproducibly synthesized in 5 steps and 31 % overall yield on the longest linear sequence. Subsequent fivefold Suzuki–Miyaura coupling with ferroceneboronic acid led to a new C5‐symmetric pentaferrocenyl molecular motor.

show abstract

Section: Resultsmentioning

confidence: 99%

Expedient Synthesis of Thioether‐Functionalized Hydrotris(indazolyl)borate as an Anchoring Platform for Rotary Molecular Machines

et al. 2018

View full text Add to dashboard Cite

show abstract

Polypyrazolylborates and Scorpionates

Fischer

2021

Comprehensive Coordination Chemistry III

View full text Add to dashboard Cite

Synthesis, Structures, and Reactivity of Yttrium Alkyl and Alkynyl Complexes with Mixed Tp^Me2/Cp Ligands

Zhang

et al. 2011

Inorg. Chem.

View full text Add to dashboard Cite

The structurally characterized Tp(Me2)-supported rare earth metal monoalkyl complex (Tp(Me2))CpYCH(2)Ph(THF) (1) was synthesized via the salt-metathesis reaction of (Tp(Me2))CpYCl(THF) with KCH(2)Ph in THF at room temperature. Treatment of 1 with 1 equiv of PhC≡CH under the same conditions afforded the corresponding alkynyl complex (Tp(Me2))CpYC≡CPh(THF) (2). Complex 1 exhibits high activity toward carbodiimides, isocyanate, isothiocyanate, and CS(2); treatment of 1 with such substrates led to the formation of a series of the corresponding Y-C(benzyl) σ-bond insertion products (Tp(Me2))CpY[(RN)(2)CCH(2)Ph] (R = (i)Pr(3a), Cy(3b), 2,6-(i)Pr-C(6)H(3)(3c)), (Tp(Me2))CpY[SC(CH(2)Ph)NPh] (4), (Tp(Me2))CpY[OC(CH(2)Ph)NPh] (5), and (Tp(Me2))CpY(S(2)CCH(2)Ph) (6) in 40-70% isolated yields. Carbodiimides and isothiocyanate can also insert into the Y-C(alkynyl) σ bond of 2 to yield complexes (Tp(Me2))CpY[(RN)(2)CC≡CPh] (R = (i)Pr(7a), Cy(7b)) and (Tp(Me2))CpY[SC(C≡CPh)NPh] (9). Further investigation results indicated that 1 can effectively catalyze the cross-coupling reactions of phenylacetylene with carbodiimides. However, treatment of o-allylaniline with a catalytic amount of 1 gave only the benzyl abstraction product (Tp(Me2))CpY(NHC(6)H(4)CH(2)CH═CH(2)-o)(THF) (10), without observation of the expected organic hydroamination/cyclization product. All of these new complexes were characterized by elemental analysis and spectroscopic properties, and their solid-state structures were also confirmed by single-crystal X-ray diffraction analysis.

show abstract

Solvent-free one-pot synthesis of thallium complexes of Tp [BH(Pz)3]− (Pz=pyrazolate) and its derivatives

Cited by 3 publications

References 25 publications

Expedient Synthesis of Thioether‐Functionalized Hydrotris(indazolyl)borate as an Anchoring Platform for Rotary Molecular Machines

Expedient Synthesis of Thioether‐Functionalized Hydrotris(indazolyl)borate as an Anchoring Platform for Rotary Molecular Machines

Polypyrazolylborates and Scorpionates

Synthesis, Structures, and Reactivity of Yttrium Alkyl and Alkynyl Complexes with Mixed Tp^Me2/Cp Ligands

Contact Info

Product

Resources

About

Solvent-free one-pot synthesis of thallium complexes of Tp [BH(Pz)3]− (Pz=pyrazolate) and its derivatives

Cited by 3 publications

References 25 publications

Expedient Synthesis of Thioether‐Functionalized Hydrotris(indazolyl)borate as an Anchoring Platform for Rotary Molecular Machines

Expedient Synthesis of Thioether‐Functionalized Hydrotris(indazolyl)borate as an Anchoring Platform for Rotary Molecular Machines

Polypyrazolylborates and Scorpionates

Synthesis, Structures, and Reactivity of Yttrium Alkyl and Alkynyl Complexes with Mixed TpMe2/Cp Ligands

Contact Info

Product

Resources

About

Synthesis, Structures, and Reactivity of Yttrium Alkyl and Alkynyl Complexes with Mixed Tp^Me2/Cp Ligands