The coordination chemistry of the proton

Kühl, Olaf

doi:10.1039/c0cs00072h

Cited by 12 publications

(6 citation statements)

References 34 publications

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“…This is influenced by the σ‐donation and π‐acceptance properties of the phosphine and amine donors. From the literature, it is known that the difference in σ‐donation properties of tertiary phosphines with different residues is small [30] . In contrast, their π‐acceptor properties change significantly, which then influences the vibrational frequency of the CO in trans position.…”

Section: Resultsmentioning

confidence: 99%

Molybdenum Tricarbonyl Complexes Supported by Linear PNP Ligands: Influence of P‐ and N‐Substituents on Relative Stability, Stereoisomerism and on the Activation of Small Molecules

Froitzheim,

Junge,

Barnehl

et al. 2023

Eur J Inorg Chem

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Series of linear tridentate PNPhPR‐ligands (R = Me, Et, Pln, Ph, Cp, Cy, iPr tBu) and molybdenum tricarbonyl complexes [Mo(CO)3PNPhPR] (R = Ph, Et, Cp, Cy, iPr) were synthesized and characterized using NMR‐, IR‐, and Raman spectroscopy as well as X‐ray crystallography. The influence of the different phosphine donor groups of the PNPhPR ligands on the bonding and activation of CO ligands is investigated. Importantly, all complexes are found to adopt a fac geometry, both in solution and in the solid state. This is in contrast to analogous complexes supported by PNHP ligands. DFT calculations reveal that the phenyl ring at the central amine function is the cause for the preferred geometry, hindering isomerization to a mer geometry.

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Section: Resultsmentioning

confidence: 99%

Molybdenum Tricarbonyl Complexes Supported by Linear PNP Ligands: Influence of P‐ and N‐Substituents on Relative Stability, Stereoisomerism and on the Activation of Small Molecules

Froitzheim,

Junge,

Barnehl

et al. 2023

Eur J Inorg Chem

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“…To this end, we set out to determine the Tolman Electronic Parameter [15] (TEP) for 2 and 8 , previously reported tin‐analogue 9 , [2] and secondary diarylphosphonite 3 . The TEP of a ligand L equals to the wavenumber of the totally symmetric (a 1 ) νCO‐mode of a complex Ni(CO) 3 (L) and is widely acknowledged as a measure of the net electron donating ability of the ligand (i. e. the sum of its σ‐donor and π‐donor/acceptor strength) and a scale for comparing this property between different ligands [16] …”

Section: Resultsmentioning

confidence: 99%

Silyl‐ and Germyl‐Substituted Diorganophosphonites

et al. 2023

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Reactions of metalated diorganophosphonite boranes with triorganosilyl and ‐germyl halides provided borane adducts of diorgano(tetryl)phosphonites. Further treatment with excess Et3N or DABCO yielded the borane‐free species (RO)2P‐ER'3 (E = Si, Ge; R, R' = alkyl, aryl). The products of all reactions were characterized by elemental analyses and NMR data, and in selected cases by MS and single‐crystal XRD studies. Reactions of selected ligands with Ni(CO)4 and selenium were shown to produce Ni(CO)3‐complexes or diorgano(tetryl)phosphonoselenoates (RO)2(R'3E)P=Se, respectively, which were identified spectroscopically but could not be isolated. Evaluation of the TEP and 1JPSe coupling constants were used for a first assessment of the electron donor properties of the new molecules.

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“…To find the most stable configuration of cationic boranes, the terminal hydrogen atoms (B–H term ) were torn off from each vertex in optimized molecules. As is widely known, bridge hydrogen atoms (B–H br –B) have an increased acidity [ 5 , 58 , 144 , 145 , 146 , 147 ]; therefore, their participation in the hydride transfer was not considered herein. For most of the small borane clusters, due to the structural rearrangements during the geometry optimization only one stable configuration of cationic boranes was found.…”

Section: Methodsmentioning

confidence: 99%

Thermodynamic Hydricity of Small Borane Clusters and Polyhedral closo-Boranes

et al. 2020

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Thermodynamic hydricity (HDAMeCN) determined as Gibbs free energy (ΔG°[H]−) of the H− detachment reaction in acetonitrile (MeCN) was assessed for 144 small borane clusters (up to 5 boron atoms), polyhedral closo-boranes dianions [BnHn]2−, and their lithium salts Li2[BnHn] (n = 5–17) by DFT method [M06/6-311++G(d,p)] taking into account non-specific solvent effect (SMD model). Thermodynamic hydricity values of diborane B2H6 (HDAMeCN = 82.1 kcal/mol) and its dianion [B2H6]2− (HDAMeCN = 40.9 kcal/mol for Li2[B2H6]) can be selected as border points for the range of borane clusters’ reactivity. Borane clusters with HDAMeCN below 41 kcal/mol are strong hydride donors capable of reducing CO2 (HDAMeCN = 44 kcal/mol for HCO2−), whereas those with HDAMeCN over 82 kcal/mol, predominately neutral boranes, are weak hydride donors and less prone to hydride transfer than to proton transfer (e.g., B2H6, B4H10, B5H11, etc.). The HDAMeCN values of closo-boranes are found to directly depend on the coordination number of the boron atom from which hydride detachment and stabilization of quasi-borinium cation takes place. In general, the larger the coordination number (CN) of a boron atom, the lower the value of HDAMeCN.

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The coordination chemistry of the proton

Cited by 12 publications

References 34 publications

Molybdenum Tricarbonyl Complexes Supported by Linear PNP Ligands: Influence of P‐ and N‐Substituents on Relative Stability, Stereoisomerism and on the Activation of Small Molecules

Molybdenum Tricarbonyl Complexes Supported by Linear PNP Ligands: Influence of P‐ and N‐Substituents on Relative Stability, Stereoisomerism and on the Activation of Small Molecules

Silyl‐ and Germyl‐Substituted Diorganophosphonites

Thermodynamic Hydricity of Small Borane Clusters and Polyhedral closo-Boranes

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