Synthesis and Characterization of Copper(I) Complexes with a Fairly Bulky Tris(pyrazolyl)hydroborate Ligand. Probing the Flexibility of the Metal-Containing Pocket Formed by the Ligand

Conry, Rebecca R.; Ji, Guanzhen; Tipton, A. Alex

doi:10.1021/ic980851w

Cited by 42 publications

(44 citation statements)

References 70 publications

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“…The copper(I) centre has a distorted tetrahedral geometry comprising the three N atoms of the [Tp * ] À anion and the C atom of the carbon monoxide molecule. The CuÐN and CuÐ C interatomic distances [CuÐN 2.033 (2)±2.054 (2) and CuÐ C 1.785 (4) A Ê ] and NÐCuÐC and CuÐCÐO interatomic angles [NÐCuÐC 124.27 (14)±124.52 (14) and CuÐCÐO 179.3 (4) ] fall within the range of values reported previously [CuÐN 2.014±2.086, CuÐC 1.752±1.808 A Ê , NÐCuÐC 119.4± 128.5 and CuÐCÐO 176.6±180.0 (Churchill et al, 1975;Conry et al, 1999;Imai et al, 1998;Kitajima et al, 1992)].…”

Section: Commentsupporting

confidence: 83%

“…The structure of the title compound [Tp * Cu(CO)]ÁMeCN {[Tp * ] À = hydrotris(3,5-dimethylpyrazol-1-yl)borate}, (I), comprises neutral [Tp * Cu(CO)] molecular units and noncoordinated acetonitrile molecules. The [Tp * Cu(CO)] molecular unit is similar to those of previously structurally characterized analogues, which differ solely in the identities of the 3,5-substituents on the pyrazole rings (Churchill et al, 1975;Conry et al, 1999;Imai et al, 1998;Kitajima et al, 1992).…”

Section: Commentsupporting

confidence: 60%

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Carbonyl[hydrotris(3,5-dimethylpyrazol-1-yl)borato]copper(I) acetonitrile solvate

Blake¹,

Carling²,

George³

et al. 2002

Acta Cryst E

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Section: Commentsupporting

confidence: 83%

Section: Commentsupporting

confidence: 60%

Carbonyl[hydrotris(3,5-dimethylpyrazol-1-yl)borato]copper(I) acetonitrile solvate

Blake¹,

Carling²,

George³

et al. 2002

Acta Cryst E

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“…The only model complexes that exhibit such low values are those derived from nonchelating imidazoles (2059 ± 2067 cm À1 ), [68] or from the anionic tris(pyrazolyl)borate ligand. [57,58,62,63] On the other hand, for complexes obtained with the neutral tris(imidazolyl)methoxymethane (n CO 2080 cm À1 ) [59] and tris(imidazolyl)phosphane (n CO 2083 ± 2086 cm À1 ) [60] tripods, the CO stretches are more energetic. Complexes 4, although structurally very similar to the biological systems, display n CO values that are % 40 cm À1 higher.…”

Section: Discussionmentioning

confidence: 99%

Biomimetic Copper(I)-CO Complexes: A Structural and Dynamic Study of a Calix[6]arene-Based Supramolecular System

et al. 2000

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Four novel calix[6]arene-based cuprous complexes are described. They present a biomimetic tris(imidazole) coordination core associated with a hydrophobic cavity that wraps the apical binding site. Each differs from the other by the methyl or ethyl substituents present on the phenoxyl groups (OR1) and on the imidazole arms (NR2) of the calix[6]arene structure. In solution, stable CO complexes were obtained. We have investigated their geometrical and dynamic properties with respect to the steric demand. IR and NMR studies revealed that, in solution, these complexes adopted two distinct conformations. The preferred conformation was dictated only by the size of the OR1 group. When R1 was an ethyl group, the complex preferentially adopted a flattened C3-symmetrical structure. The corresponding helical enantiomers were in conformational equilibrium, which, however, was slow on the 1H NMR time scale at -80 degrees C. When R1 was a methyl group, the low-temperature NMR spectra revealed the partial inclusion of one tBu group. The complex wobbled between three dissymmetric but equivalent conformations. Hence, small differences in the steric demand of the calixarene's skeleton changed the geometry and dynamics of the system. Indeed, this supramolecular control was promoted by the strong conformational coupling between the metal center and the host structure. Interestingly, this was not only the result of a covalent preorganization, but also stemmed from weak interactions within the hydrophobic pocket. The vibrational spectra of the bound CO were revealed to be a sensitive gauge of this supramolecular behavior, similar to copper proteins in which allosteric effects are common.

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“…Some of the interesting ligands include the dipicolinate [6], tris-(benzyltriazolylmethyl)amine (TBTA) [7], the crowded tetradentatetris(2-dioctadecylaminoethyl)amine (C186tren) [8], tris(triazolyl)methanol (TBTM) [9], and tris(pyrazolyl)methane (Tpm)-molecules which are found to be effective in the formation of N-sulfonyl-1,2,3-triazoles from N-sulfonylazides and alkynes ( Figure 1) [10]. The well-known homoscorpionate ligands based on tris(pyrazolyl)hydroborate and bis(pyrazolyl)dihydroborate anions tris(pyrazolyl)hydroborate (HB(pz) 3 − ) and bis(pyrazolyl)hydroborate (H 2 B(pz) 2 − ) are among the powerful and familiar polydentate nitrogen-containing species that have demonstrated to be versatile ligands useful for the preparation of copper(I) complexes [11][12][13][14][15][16][17] (Figure 1). The principal feature in all poly(pyrazolyl)borate complexes is the formation of the six-membered ring that stabilizes the copper(I) ion [18].…”

Section: Introductionmentioning

confidence: 99%

“…(Right) Packing view showing the interactions involving the NH2 group. Selected bond lengths and angles (Å°): N(1)-N(2), 1.3409(19); N(1)-C(5), 1.342(2); N(1)-C(10), 1.468(2); N(2)-N(3), 1.3211(19); N(3)-C(4), 1.367(2); C(4)-C(5), 1.373(2); N(2)-N(1)-C(5), 111.07(14); N(3)-N(2)-N(1), 106.95(14); N(2)-N(3)-C(4), 109.14(13); N(3)-C(4)-C(5), 107.43(14); and N(1)-C(5)-C(4), 105.41(15).…”

mentioning

confidence: 99%

Clicking Azides and Alkynes with Poly(pyrazolyl)borate-Copper(I) Catalysts: An Experimental and Computational Study

et al. 2019

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The synthesis of 1,4-disubstituted-1,2,3-triazoles under a copper(I)-catalyzed azide–alkyne cycloaddition (CuAAC) regime was accomplished in high yields and a regioselective manner by using two homoscorpionate poly(pyrazolyl)borate anions: tris(pyrazolyl)hydroborate (HB(pz)3−) and bis(pyrazolyl)hydroborate (H2B(pz)2−), which stabilized in situ the catalytically active copper (I) center. The [3+2] cycloaddition (32CA) reactions took place under strict click conditions, including room temperature and a mixture of environmentally benign solvents such as water/ethanol in a 1:1 (v/v) ratio. These click chemistry conditions were applied to form complex 1,2,3-triazoles-containing sugar moieties, which are potentially relevant from a biological point of view. Computational modeling carried out by DFT methodologies at the B3LYP/6-31G(d) level showed that the coordination of poly(pyrazolyl)borate-copper(I) to alkyne groups produced relevant changes in terms of generating a high polar copper(I)-acetylide intermediates. The analysis of the global and local reactivity indices explains correctly the role of poly(pyrazolyl)borate ligands in the stabilization and activation of the copper(I) catalyst in the studied 32CA reactions.

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Synthesis and Characterization of Copper(I) Complexes with a Fairly Bulky Tris(pyrazolyl)hydroborate Ligand. Probing the Flexibility of the Metal-Containing Pocket Formed by the Ligand

Cited by 42 publications

References 70 publications

Carbonyl[hydrotris(3,5-dimethylpyrazol-1-yl)borato]copper(I) acetonitrile solvate

Carbonyl[hydrotris(3,5-dimethylpyrazol-1-yl)borato]copper(I) acetonitrile solvate

Biomimetic Copper(I)-CO Complexes: A Structural and Dynamic Study of a Calix[6]arene-Based Supramolecular System

Clicking Azides and Alkynes with Poly(pyrazolyl)borate-Copper(I) Catalysts: An Experimental and Computational Study

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