Hydride‐Triel Bonds

Jabłoński, Mirosl̷aw

doi:10.1002/jcc.25178

Cited by 38 publications

(78 citation statements)

References 72 publications

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“…The analysis of the molecular graphs depicted in Figure shows that intermolecular bond paths are readily formed between highly electronegative atoms, whereas the “reluctance” to boron atom is clearly visible . The former behavior is well known,,,,, while the latter one is in contradiction with the fact that boron atom eagerly creates donor‐acceptor triel bonds of various types, e. g. H

^{δ -} \dots

B (charge‐inverted hydrogen bonds),, N⋅⋅⋅B, O⋅⋅⋅B,

σ \dots

π \dots

B .…”

Section: Resultsmentioning

confidence: 98%

On the Uselessness of Bond Paths Linking Distant Atoms and on the Violation of the Concept of Privileged Exchange Channels

Jabłoński

2019

ChemistryOpen

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We refer to frequently used determinants suggesting dominant interactions between distant atoms in various dimers. First of all, we show, against the still-prevailling opinion, that, in general, bond paths have nothing in common with dominant intermolecular interactions and therefore they are useless in such cases. Quite the contrary, reliable information about dominant intermolecular interactions can be obtained by means of electrostatic potential maps, which very convincingly explain mutual orientation of molecules in a dimer. For the first time, numerous examples of interactions that violate both the concept of privileged exchange channels proposed by Pendás and his collaborators as well as inequalities obtained by Tognetti and Joubert for the β parameter related to secondary interactions are presented. The possible cause of this violation is suggested. We also show that the so-called counterintuitive bond paths result from quite natural behavior of the electron density gradient vector, i. e. searching for those areas of space that are characterized by large values of electron density or the most expanded its distributions.[a] Dr.

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^{δ -} \dots

B (charge‐inverted hydrogen bonds),, N⋅⋅⋅B, O⋅⋅⋅B,

σ \dots

π \dots

B .…”

Section: Resultsmentioning

confidence: 98%

On the Uselessness of Bond Paths Linking Distant Atoms and on the Violation of the Concept of Privileged Exchange Channels

Jabłoński

2019

ChemistryOpen

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“…This may reflect their weakness, but despite the assumption that the presence of bond path on the molecular graph confirms the presence of a binding interaction, there is a growing number of reports clearly showing that for interactions between more distant atoms it is not necessary. [10g], , Although the lack of bond paths and the corresponding bond critical points (BCPs) characterizing the H ··· Al interactions in 5a and 5b prevents a direct comparison of some QTAIM parameters important for the binding analysis, further information about these interactions can be obtained in an indirect manner by analyzing values obtained for BCPs of Ge–H bonds. Two QTAIM‐based parameters in particular describe the bond strength, the electron density at BCP and the delocalization index (in this case of Ge and H atomic basins) .…”

Section: Resultsmentioning

confidence: 99%

“…Important parameters describing the Ge-H···Al group in closed and open forms of 5a and 5b (distances in pm, angles and pyramidalization index in degrees, wave numbers in cm -1 , interaction energy in kcal/mol). (2), Al1···H1 293 (3), Ge1-C11 194 (1), Ge1-C21 192 (2), Ge1-C31 195.3 (2), Ge1-H1 154 (3), C31-C32 134.2(4), Ge1-C31-Al1 108.2 (1).…”

Section: Hydroalumination Of Alkynylgermanesmentioning

confidence: 99%

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Aluminium Functionalized Germanes: Intramolecular Activation of Ge–H Bonds, Formation of a Dihydrogen Bond and Facile Hydrogermylation of Unsaturated Substrates

et al. 2019

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A series of alkenylhydrogermanes, RR′(H)Ge‐C(AlR′′2)=C(H)‐tBu [4a, R = R′ = Mes, R′′ = tBu; 4b, R = R′ = Mes, R′′ = CH(SiMe3)2; 5a, R = R′′ = tBu, R′ = CH2CH2tBu; 5b, R = tBu, R′ = CH2CH2tBu, R′′ = CH(SiMe3)2], was synthesized by hydroalumination of the respective alkynylgermanes, RR′(H)Ge‐C≡C‐tBu 3, with R′′2Al–H [R′′ = tBu, CH(SiMe3)2]. In the solid state compound 5b showed a contact between Al and the Ge bound H atom (293 pm) which according to quantum chemical calculations results in Ge–H bond activation. In case of less bulky substituents on Al (5a, R′′ = tBu) a mixture of isomers was observed that reacted with Et2NH to yield the simple Lewis acid‐base adduct [(tBu)(tBuCH2CH2)(H)Ge‐C(AltBu2)=C(H)‐tBu](HNEt2) (6). 6 features a dihydrogen bond (Ge–H···H–N) as evident from typical downfield (N–H) and high‐field (Ge–H) shifts in the NMR spectrum, red shifts of νGe‐H and νN‐H in the IR spectrum, a short H···H contact (210 pm) in the solid state and a bond critical point between both H atoms. The presence of a hard Lewis‐acidic Al atom in geminal position to the Ge–H bond in 5a facilitates reactions with Ph2CO, OC4H8N‐C≡N and Ph–NCO under surprisingly mild conditions by hydrogermylation of the heteronuclear π‐bonds and formation of four‐membered Ge–O/N–Al–C (7, 9) or six‐membered Ge–N–C–O–Al–C (8) heterocycles. Reaction with Ph–C≡C–H afforded the cis‐addition product 10, in which the α‐C atom of the new alkenyl group showed a close contact [258.3(2) pm] to the Al atom.

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“…There are also exceptional cases wherein a tetravalent Tr atom can generate a σ-hole [57]. This TrB has generated sufficient interest so as to be the focus of a number of prior quantum chemical studies [58][59][60][61][62][63][64][65][66][67][68][69][70][71][72][73]. Our own earlier study of the TrB [73] in complexes of TrR 3 (Tr = B, Al, Ga; R = H, F, Cl, Br, CH 3 ) with pyrazine provides some information about the influence of various substituents on the energy, geometry, and properties of this interaction.…”

Section: Introductionmentioning

confidence: 99%

Competition between Intra and Intermolecular Triel Bonds. Complexes between Naphthalene Derivatives and Neutral or Anionic Lewis Bases

2020

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: A TrF2 group (Tr = B, Al, Ga, In, Tl) is placed on one of the α positions of naphthalene, and its ability to engage in a triel bond (TrB) with a weak (NCH) and strong (NC−) nucleophile is assessed by ab initio calculations. As a competitor, an NH2 group is placed on the neighboring Cα, from which point it forms an intramolecular TrB with the TrF2 group. The latter internal TrB reduces the intensity of the π-hole on the Tr atom, decreasing its ability to engage in a second external TrB. The intermolecular TrB is weakened by a factor of about two for the smaller Tr atoms but is less severe for the larger Tl. The external TrB can be quite strong nonetheless; it varies from a minimum of 8 kcal/mol for the weak NCH base, up to as much as 70 kcal/mol for CN−. Likewise, the appearance of an external TrB to a strong base like CN− lessens the ability of the Tr to engage in an internal TrB, to the point where such an intramolecular TrB becomes questionable.

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Hydride‐Triel Bonds

Cited by 38 publications

References 72 publications

On the Uselessness of Bond Paths Linking Distant Atoms and on the Violation of the Concept of Privileged Exchange Channels

On the Uselessness of Bond Paths Linking Distant Atoms and on the Violation of the Concept of Privileged Exchange Channels

Aluminium Functionalized Germanes: Intramolecular Activation of Ge–H Bonds, Formation of a Dihydrogen Bond and Facile Hydrogermylation of Unsaturated Substrates

Competition between Intra and Intermolecular Triel Bonds. Complexes between Naphthalene Derivatives and Neutral or Anionic Lewis Bases

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