The interplay of proton accepting and hydride donor abilities in the mechanism of step-wise boron hydrides alcoholysis

Golub, Igor E.; Filippov, Oleg A.; Gulyaeva, Ekaterina S.; Gutsul, Evgenii I.; Belkova, Natalia V.

doi:10.1016/j.ica.2016.10.037

Cited by 14 publications

(22 citation statements)

References 67 publications

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“…As the result the activation energies of proton‐hydride transfer decrease on going from n= 0 to n= 3 (Figure ). Corresponding transition states become earlier and feature shorter B−H and O−H distances together with longer H−H bonds for higher n …”

Section: Reaction Mechanismsmentioning

confidence: 99%

“…Hence, the formation of H 2 molecule and [BH 3 (OR)] − product is the result of simultaneous proton and hydride transfer within the DHB complex. The reaction proceeds further in a similar manner yielding ultimately [M(OR) 4 ] − species; the first proton transfer is the rate‐limiting step …”

Section: Reaction Mechanismsmentioning

confidence: 99%

“…Green: BH 4 ] − , blue: [BH 3 OR] − , red: [BH 2 (OR) 2 ] − , black: [BH(OR) 3 ] − . Data from reference .…”

Section: Reaction Mechanismsmentioning

confidence: 99%

“…Also, systems with relatively low barriers could be found in the central part of the graph (at 30–70 % of the electron density depletion). They are exemplified by Cp*Mo(PMe 3 ) 2 (CO)H/(CF 3 COOH) 2 (in which the OH bond is already strongly activated in the DHB complex), and BH(OR) 3 /HOR (OH bonds) as well as by both MH bonds of bimetallic complex (PCP)PdH/CpWH(CO) 3 …”

Section: Electronic and Structural Changes In Transition Statementioning

confidence: 99%

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Z−H Bond Activation in (Di)hydrogen Bonding as a Way to Proton/Hydride Transfer and H₂ Evolution

Belkova

Filippov

Shubina

2017

Chemistry A European J

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The ability of neutral transition-metal hydrides to serve as a source of hydride ion H or proton H is well appreciated. The hydride ligands possessing a partly negative charge are proton accepting sites, forming a dihydrogen bond, M-H ⋅⋅⋅ HX (M=transition metal or metalloid). On the other hand, some metal hydrides are able to serve as a proton source and give hydrogen bond of M-H ⋅⋅⋅X type (X=organic base). In this paper we analyse recent works on transition-metal and boron hydrides showing i) how formation of an intermolecular complex between the reactants changes the Z-H (M-H and X-H) bond polarity and ii) what is the implication of such activation in the mechanisms of hydrides reactions.

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Section: Reaction Mechanismsmentioning

confidence: 99%

Section: Reaction Mechanismsmentioning

confidence: 99%

“…Green: BH 4 ] − , blue: [BH 3 OR] − , red: [BH 2 (OR) 2 ] − , black: [BH(OR) 3 ] − . Data from reference .…”

Section: Reaction Mechanismsmentioning

confidence: 99%

Section: Electronic and Structural Changes In Transition Statementioning

confidence: 99%

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Z−H Bond Activation in (Di)hydrogen Bonding as a Way to Proton/Hydride Transfer and H₂ Evolution

Belkova

Filippov

Shubina

2017

Chemistry A European J

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“…Our studies of intermolecular interactions of BH4 − [65,66] and several metal tetrahydroborates [67][68][69][70] with proton donors have shown the versatility of dihydrogen bonded (DHB) complexes formed and their crucial role in the reactivity of these compounds. In particular, we have shown that the formation of bifurcate DHB complexes involving both bridging and terminal hydride hydrogens of (Ph3P)2Cu(η 2 -BH4) (Scheme 2) is prerequisite for the subsequent proton transfer and dimerization to occur [67].…”

Section: Introductionmentioning

confidence: 99%

Binuclear Copper(I) Borohydride Complex Containing Bridging Bis(diphenylphosphino) Methane Ligands: Polymorphic Structures of [(µ2-dppm)2Cu2(η2-BH4)2] Dichloromethane Solvate

et al. 2017

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Bis(diphenylphosphino)methane copper(I) tetrahydroborate was synthesized by ligands exchange in bis(triphenylphosphine) copper(I) tetrahydroborate, and characterized by XRD, FTIR, NMR spectroscopy. According to XRD the title compound has dimeric structure, [(µ 2 -dppm) 2 Cu 2 (η 2 -BH 4 ) 2 ], and crystallizes as CH 2 Cl 2 solvate in two polymorphic forms (orthorhombic, 1, and monoclinic, 2) The details of molecular geometry and the crystal-packing pattern in polymorphs were studied. The rare Twisted Boat-Boat conformation of the core Cu 2 P 4 C 2 cycle in 1 is found being more stable than Boat-Boat conformation in 2.

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Comprehensive Insight into the Hydrogen Bonding of Silanes

Voronova

Golub

Павлов

et al. 2018

Chemistry An Asian Journal

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The interaction of a set of mono-, di- and trisubstituted silanes with OH proton donors of different strength was studied by variable temperature (VT) FTIR and NMR spectroscopies at 190-298 K. Two competing sites of proton donors coordination: SiH and π-density of phenyl rings-are revealed for phenyl-containing silanes. The hydrogen bonds SiH⋅⋅⋅HO and OH⋅⋅⋅π(Ph) are of similar strength, but can be distinguished in the ν range: the ν vibrations appear at lower frequencies while OH⋅⋅⋅π(Ph) complexes give Si-H vibrations shifted to higher frequency. The calculations showed the manifold picture of the noncovalent interactions in hydrogen-bonded complexes of phenylsilanes. As OH⋅⋅⋅HSi bonds are weak, the other noncovalent interactions compete in the stabilization of the intermolecular complexes. Still, the structural and electronic parameters of "pure" DHB complexes of phenylsilanes are similar to those of Et SiH.

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The interplay of proton accepting and hydride donor abilities in the mechanism of step-wise boron hydrides alcoholysis

Cited by 14 publications

References 67 publications

Z−H Bond Activation in (Di)hydrogen Bonding as a Way to Proton/Hydride Transfer and H₂ Evolution

Z−H Bond Activation in (Di)hydrogen Bonding as a Way to Proton/Hydride Transfer and H₂ Evolution

Binuclear Copper(I) Borohydride Complex Containing Bridging Bis(diphenylphosphino) Methane Ligands: Polymorphic Structures of [(µ2-dppm)2Cu2(η2-BH4)2] Dichloromethane Solvate

Comprehensive Insight into the Hydrogen Bonding of Silanes

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The interplay of proton accepting and hydride donor abilities in the mechanism of step-wise boron hydrides alcoholysis

Cited by 14 publications

References 67 publications

Z−H Bond Activation in (Di)hydrogen Bonding as a Way to Proton/Hydride Transfer and H2 Evolution

Z−H Bond Activation in (Di)hydrogen Bonding as a Way to Proton/Hydride Transfer and H2 Evolution

Binuclear Copper(I) Borohydride Complex Containing Bridging Bis(diphenylphosphino) Methane Ligands: Polymorphic Structures of [(µ2-dppm)2Cu2(η2-BH4)2] Dichloromethane Solvate

Comprehensive Insight into the Hydrogen Bonding of Silanes

Contact Info

Product

Resources

About

Z−H Bond Activation in (Di)hydrogen Bonding as a Way to Proton/Hydride Transfer and H₂ Evolution

Z−H Bond Activation in (Di)hydrogen Bonding as a Way to Proton/Hydride Transfer and H₂ Evolution