Bitopic Bis- and Tris(1-pyrazolyl)borate Ligands:  Syntheses and Structural Characterization

Bieller, Susanne; Zhang, Fan; Bolte, Michael; Bats, Jan W.; Lerner, Hans‐Wolfram; Wagner, Mat­thias

doi:10.1021/om049954e

Cited by 71 publications

(64 citation statements)

References 13 publications

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“…[33][34][35] So far, the main focus was on homoditopic ligand systems consisting of two identical scorpionate units that are bridged by organometallic or aromatic linkers. Replacement of pyrazolyl rings by thioether moieties allows to extend the research to heteroditopic scorpionate ligands in which the two donor sites are no longer the same so that the two coordinated metal centers will show different reactivity.…”

Section: A C H T U N G T R E N N U N G (Ch 2 Sme)]mentioning

confidence: 99%

Copper Complexes of Mono‐ and Ditopic [(Methylthio)methyl]borates: Missing Links and Linked Systems En Route to Copper Enzyme Models

Ruth

Tüllmann

Vitze

et al. 2008

Chemistry A European J

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TMEDA-free (TMEDA: tetramethylethylenediamine) LiCH(2)SMe is a suitable reagent for the selective introduction of (methylthio)methyl groups into PhBBr(2) and its p-silylated derivative Me(3)Si--C(6)H(4)--BBr(2). The resulting compounds, R*--C(6)H(4)--B(Br)(CH(2)SMe) (R*=H: 2; R*=SiMe(3): 7) and PhB(CH(2)SMe)(2) (3), form cyclic dimers through B--S adduct bonds in solution and in the solid state. Compounds 2 and 3 have successfully been used for preparing the (N(2)S) scorpionate [PhBpz(2)(CH(2)SMe)](-) ([5](-)) (pz: pyrazol-1-yl) and the (NS(2)) scorpionate [PhBpz(CH(2)SMe)(2)](-), respectively. Compound 7 proved to be an excellent building block for the heteroditopic poly(pyrazol-1-yl)borate p-[pz(3)B--C(6)H(4)--Bpz(2)(CH(2)SMe)](2-) ([10](2-)) that mimics the two ligation sites of the copper enzymes peptidylglycine alpha-hydroxylating monooxygenase and dopamine beta-monooxygenase. Treatment of the monotopic tripod [5](-) with CuCl and CuBr(2) results in the formation of complexes K[Cu(5)(2)] and [Cu(5)(2)]. An X-ray crystallography study of K[Cu(5)(2)] revealed a tetrahedral (N(2)S(2)) coordination environment for the Cu(I) ion, whereas the Cu(II) ion of [Cu(5)(2)] possesses a square-pyramidal (N(4)S) ligand sphere (S-atom in the axial position). The remarkable redox properties of K[Cu(5)(2)] and [Cu(5)(2)] have been assessed by cyclic voltammetry and quantum chemical calculations. The reaction of K[Cu(5)(2)] with dry air leads to the Cu(II) species [Cu(5)(2)] and to a tetranuclear Cu(II) complex featuring [PhB(O)pz(2)](2-) ligands. Addition of CuCl to K(2)[10] gives the complex K(3)[Cu(10)(2)] containing two ligand molecules per Cu(I) center. The Cu(I) ion binds to both heteroscorpionate moieties and thereby establishes a coordination environment similar to that of the Cu(I) ion in K[Cu(5)(2)].

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Section: A C H T U N G T R E N N U N G (Ch 2 Sme)]mentioning

confidence: 99%

Copper Complexes of Mono‐ and Ditopic [(Methylthio)methyl]borates: Missing Links and Linked Systems En Route to Copper Enzyme Models

Ruth

Tüllmann

Vitze

et al. 2008

Chemistry A European J

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“…(10) generally stops at the di-substitution stage. Polytopic poly(pyrazol-1-yl)borate ligands have shown great potential for the preparation of coordination polymers [107][108][109], multiple-decker sandwich complexes [110][111][112][113], metallomacrocycles [114], dinuclear complexes with cooperating metal ions [115][116][117][118], and metalloenzyme models [119]. As with the KBH 4 reaction, the pyrazole 3(5)-substituent ends up in the 3-position.…”

Section: Synthesis Of Poly(pyrazolyl)boratesmentioning

confidence: 99%

Synthesis and Properties of Poly(pyrazolyl)borate and Related Boron-Centered Scorpionate Ligands. Part A: Pyrazole-Based Systems

Santini¹,

Pellei²,

Lobbia³

et al. 2010

MROC

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This review is intended to cover the developments in the chemistry of poly(azolyl)borates through the years 2000-2008, based on the main synthetic methods, coordination properties, spectroscopic and structural features of this important class of ligands. The subject matter is the chemistry of substituted bis-, tris-and tetrakis-(pyrazolyl)borate ligands. In this review we provide essential information to allow the reader to probe more deeply into the main aspects of the chemistry of these fascinating and flexible ligands. This review would also demonstrate the enormous potential of poly(pyrazolyl)borates chemistry, as also the future perspectives in this field.

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“…Compounds bearing several heterocyclic moieties can act as multidentate ligands for the construction of metal-organic frameworks (MOFs) [1][2][3][4]. Constant design of new MOFs is stimulated by their high capacity for gas storage [5][6][7], photophysical properties [8], sensor capabilities [9] and excellent catalytic performance [10].…”

Section: Introductionmentioning

confidence: 99%

Study of product composition of the reaction between 1,1,2,2-tetrabromoethane and imidazole or 1,2,4-triazole in a superbasic medium

Kluchenko

Kadirov

Kuznetsova

et al. 2015

Proceedings of the 19th International Electronic Conference on Synthetic Organic Chemistry

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Influence of reagent ratio on the composition of products of the reaction between 1,1,2,2-tetrabromoethane and imidazole or 1,2,4-triazole in a superbasic medium (potassium hydroxide -dimethyl sulfoxide) was investigated using GC/MS technique. It was found that nucleophilic substitution reaction is always accompanied by elimination reactions (dehydrobromination and debromination). In addition to 1,1,2,2-tetra(azol-1-yl)ethane, 1,1,2-tri(azol-1-yl)ethenes and 1,2-di(azol-1-yl)ethenes, as well as 1,2-di(azol-1-yl)-1-bromoethenes were detected. Reaction pathway that explains the formation of all major products was proposed.

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Bitopic Bis- and Tris(1-pyrazolyl)borate Ligands: Syntheses and Structural Characterization

Cited by 71 publications

References 13 publications

Copper Complexes of Mono‐ and Ditopic [(Methylthio)methyl]borates: Missing Links and Linked Systems En Route to Copper Enzyme Models

Copper Complexes of Mono‐ and Ditopic [(Methylthio)methyl]borates: Missing Links and Linked Systems En Route to Copper Enzyme Models

Synthesis and Properties of Poly(pyrazolyl)borate and Related Boron-Centered Scorpionate Ligands. Part A: Pyrazole-Based Systems

Study of product composition of the reaction between 1,1,2,2-tetrabromoethane and imidazole or 1,2,4-triazole in a superbasic medium

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