Reactivity of copper(I) tetrahydroborates toward carbon dioxide and carbonyl sulfide. Structure of (triphos)Cu(.eta.1-O2CH)

Bianchini, Claudio; Ghilardi, Carlo A.; Meli, Andrea; Midollini, Stefano; Orlandini, Annabella

doi:10.1021/ic00200a025

Cited by 72 publications

(42 citation statements)

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“…28,29 The low-field position of phosphorus resonance supports the formation of the [(triphos)Cu] + cation characterized in ref. 30 in the presence of weakly coordinating counter ions. This behavior is different from that observed for (Ph 3 P) 2 Cu(η 2 -BH 4 ), which gives a dimeric product [{(Ph 3 P) 2 Cu} 2 (μ,η 2 :η 2 -BH 4 )] + [(RO) 4 B] − upon reaction with alcohols.…”

Section: Spectral Investigation Of the Proton Transfer Reactionmentioning

confidence: 99%

Two pathways of proton transfer reaction to (triphos)Cu(η¹-BH₄) via a dihydrogen bond [triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane]

et al. 2016

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The interaction of the η(1)-tetrahydroborate copper(i) complex (triphos)Cu(η(1)-BH4) () with proton donors [CF3CH2OH (TFE), (CF3)2CHOH (HFIP), (CF3)3COH (PFTB), PhOH, p-NO2C6H4OH (PNP), p-NO2C6H4N[double bond, length as m-dash]NC6H4OH (PNAP), CF3OH] was a subject of a combined IR spectroscopic and theoretical investigation. Spectral (Δν) and thermodynamic (ΔH) parameters of dihydrogen bond (DHB) formation were determined experimentally. The terminal hydride ligand (characterized by the basicity factor Ej(BH) = 0.87 ± 0.01) is found to be a site of proton transfer which begins with nucleophilic substitution of BH4(-) by the alcohol oxygen atom on the copper center (BH pathway). The activation barrier computed for (CF3)2CHOH in CH2Cl2 - ΔG = 20.6 kcal mol(-1) - is in good agreement with the experimental value (ΔG = 20.0 kcal mol(-1)). An abnormal dependence of the reaction rate on the proton donor strength found experimentally in dichloromethane is explained computationally on the basis of the variation of the structural and energetic details of this process with the proton donor strength. In the second reaction mechanism found (CuH pathway), DHB complexes with the initial ROH coordination to the bridging hydride lead to B-Hbr bond cleavage with BH3 elimination. "Copper assistance" via the CuO interaction is not involved. This mechanism can be evoked to explain the occurrence of proton transfer in coordinating solvents.

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Section: Spectral Investigation Of the Proton Transfer Reactionmentioning

confidence: 99%

Two pathways of proton transfer reaction to (triphos)Cu(η¹-BH₄) via a dihydrogen bond [triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane]

et al. 2016

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“…To date, the only complexes of this type whose structures have been determined are [(PPh3)2-CU( 02CH)I * and [ (triphos)C~( 02CH)I. 28 Synthetic methods which have been reported for the preparation of copper(1) and silver(1) carboxylates and their adducts present some experimental difficulties, particularly in the case of the formates. Thus, both copper(1) and silver(1) formate are extraordinarily sensitive to reduction to the corresponding metal.…”

Section: -28 and Structures Have Been Reported In Sbmementioning

confidence: 99%

Crystal Structure, Infrared and Solid State CP MAS NMR Characterization of [(PPh3)2AgO2CH] and of [(PPh3)2AgO2CH].cntdot.2HCO2H, a Complex of the H-Bonded [H2(HCO2)3]- Species

Bowmaker¹,

Effendy²,

Hanna³

et al. 1995

J. Phys. Chem.

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Bis(triphenylphosphine)silver(I) formate and its diformic acid adduct, [(PPh3)2Ag02CH]*2CHO2H have been prepared and characterized by infrared spectroscopy, solid state CP MAS 13C and 31P NMR spectroscopy, and single-crystal X-ray diffraction. Crystals of [(PPh3)2Ag02CH] are isomorphous, with [(PPh3)2Cu02CH]crystallizing as discrete monomeric units in the monoclinic space group CYc with a 2-fold crystallographic axis of symmetry through the bisector of the P-Ag-P angle and the anion. The formate anion is symmetrically coordinated to the silver with an Ag-0 distance of 2.425(3) A. The Ag-P distance is 2.4261(7) A, and the P-Ag-P angle 127.37(3)". Crystals of the diformic acid adduct belong to the orthorhombic space group Pnma, in which the PPh3 ligands are related by a crystallographic mirror plane containing the silver atom, the formate anions, and the two molecules of formic acid. The anion is unsymmetrically coordinated with the Ag-0 distances of 2.550(7) and 2.713(8) A, seemingly a consequence of strong hydrogen bond formation with each of the formic acid molecules, with 0-0 distances of 2.56(1) and 2.50(1) A. Although the Ag-P distance of 2.426(2) A is unchanged from that of [(PPh3)2Ag02CH], the P-Ag-P angle increases to 147.86-(7)", the largest yet recorded for the [(PPh3)2Ag]+ cation. The compound can be regarded as a complex between the [(PPh3)2Aglf cation and the previously unknown doubly H-bonded [H2(HC02)3]-"triformate" anion. Infrared bands due to this anion are assigned and discussed in relation to the metal-ligand and H-bonding in the complexes. The solid state cross-polarization magic angle spinning (CP MAS) I3C NMR spectra of [(PPh3)2Ag02CH] shows a single carbonyl peak at 169.7 ppm, while for the formic acid adduct, three distinct peaks at 163.5, 166.1, and 169.4 are observable. Simple doublets arising from 'J(AgP) coupling are observed in the 31P solid state NMR spectra of both complexes with a line spacing of 432 Hz for [(PPh&-AgOzCH] and 5 17 Hz for [(PPh3)zAg02CHIo2HCO2H.

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“…Dithiocarbamates represent an interesting class of dithio ligand and their complexes exhibit interesting molecular conducting, magnetic and optical properties [2][3][4][5]. Dithiocarbamato ligands show unsymmetrical bidentate or monodentate coordination behavior which help us in the study of structural chemistry.…”

Section: Introductionmentioning

confidence: 99%

Syntheses, crystal structures and photoluminescent properties of new homoleptic and heteroleptic zinc(II) dithiocarbamato complexes

et al. 2015

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Reactivity of copper(I) tetrahydroborates toward carbon dioxide and carbonyl sulfide. Structure of (triphos)Cu(.eta.1-O2CH)

Cited by 72 publications

References 1 publication

Two pathways of proton transfer reaction to (triphos)Cu(η¹-BH₄) via a dihydrogen bond [triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane]

Two pathways of proton transfer reaction to (triphos)Cu(η¹-BH₄) via a dihydrogen bond [triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane]

Crystal Structure, Infrared and Solid State CP MAS NMR Characterization of [(PPh3)2AgO2CH] and of [(PPh3)2AgO2CH].cntdot.2HCO2H, a Complex of the H-Bonded [H2(HCO2)3]- Species

Syntheses, crystal structures and photoluminescent properties of new homoleptic and heteroleptic zinc(II) dithiocarbamato complexes

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Reactivity of copper(I) tetrahydroborates toward carbon dioxide and carbonyl sulfide. Structure of (triphos)Cu(.eta.1-O2CH)

Cited by 72 publications

References 1 publication

Two pathways of proton transfer reaction to (triphos)Cu(η1-BH4) via a dihydrogen bond [triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane]

Two pathways of proton transfer reaction to (triphos)Cu(η1-BH4) via a dihydrogen bond [triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane]

Crystal Structure, Infrared and Solid State CP MAS NMR Characterization of [(PPh3)2AgO2CH] and of [(PPh3)2AgO2CH].cntdot.2HCO2H, a Complex of the H-Bonded [H2(HCO2)3]- Species

Syntheses, crystal structures and photoluminescent properties of new homoleptic and heteroleptic zinc(II) dithiocarbamato complexes

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Two pathways of proton transfer reaction to (triphos)Cu(η¹-BH₄) via a dihydrogen bond [triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane]

Two pathways of proton transfer reaction to (triphos)Cu(η¹-BH₄) via a dihydrogen bond [triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane]