Attaching Be or Mg to BH3 results in the formation of BeBH3 and MgBH3 molecules capable of forming stable anions

Anusiewicz, Iwona; Skurski, Piotr

doi:10.1016/j.cplett.2018.03.007

Cited by 7 publications

(14 citation statements)

References 46 publications

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“…In our earlier work, 24 we found that BeBH 3 dissociating into Be + BH 3 had a ΔG 298 of 10.68 kcal/mol. D. Negative Ions.…”

Section: Resultsmentioning

confidence: 69%

“…In searching for the lowest energy structures, we did consider geometries such as H–Mg–AlH 2 but in all cases such structures were found to be considerably higher in energy than those discussed here. In ref we studied the BH 3 , AlH 3 , and GaH 3 fragments and their anions and in ref we studied Be and Mg bonded to BH 3 and the anions of these two complexes, and we will include some discussion of these species in the present work to offer comparisons. For some of the species, we also found higher energy local minima having θ values of opposite sign to those of our reported global minima.…”

Section: Resultsmentioning

confidence: 99%

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Unusual and Conventional Dative Bond Formation by s² Lone Pair Donation from Alkaline Earth Metal Atoms to BH₃, AlH₃, and GaH₃

et al. 2020

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Using ab initio electronic structure methods with flexible atomic orbital basis sets, we examined the nature of the bonding arising from donation of an ns2 electron pair on an alkaline earth atom (Mg or Ca) into a vacant n′p orbital on the group 13 atom of BH3, AlH3, or GaH3. We also examined what happens when an excess electron is attached to form corresponding molecular anions. Although the geometries of MgBH3, MgAlH3, MgGaH3, and CaBH3 are found to be much as one would expect for datively bound molecules, CaAlH3 and CaGaH3 were found to have very unusual geometries in that their Al–H or Ga–H bonds are directed toward the Ca atom rather than away, as in the other compounds. Internal electrostatic Coulomb attractions between the partially positively charged Ca center and the partially negatively charged H centers were suggested as a source of these unusual geometries. The other novel finding is that the electron affinities (EAs) of all six M′–MH3 species lie in the 0.7–1.0 eV range, which is suggestive of ionic electronic structures for the neutrals even though the partial charges on the alkaline earth centers are as low as 0.3 atomic units. Partial positive charge on the alkaline earth atoms combined with substantial electron affinities of the BH3, AlH3, and GaH3 groups, but only when distorted from planar geometries, were suggested to be the primary contributors to the large EAs.

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“…In our earlier work, 24 we found that BeBH 3 dissociating into Be + BH 3 had a ΔG 298 of 10.68 kcal/mol. D. Negative Ions.…”

Section: Resultsmentioning

confidence: 69%

Section: Resultsmentioning

confidence: 99%

Unusual and Conventional Dative Bond Formation by s² Lone Pair Donation from Alkaline Earth Metal Atoms to BH₃, AlH₃, and GaH₃

et al. 2020

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“…The nature of the Na‒B bond in NaBH 3 − has been perhaps the most controversial topic among the chemical bond community since the beginning of the COVID-19 era 1 – 7 . Previous studies on this bond and M‒B bonds of other [M n+ BH 3 ] 2‒n complexes (M: Li, Na, K, Mg, and Ca) within the context of the most sophisticated bond analysis methodologies have revealed that these bonds are indeed unique 4 – 8 . In a recent work Radenkovic et al 6 used breathing orbital valence bond (BOVB) analysis and verified that only −3.6 kcal.mol − 1 , i.e., 9.9% of the bond dissociation energy (−36.4 kcal.mol − 1 ) in Na‒B bond of NaBH 3 − originates from the spin-exchange covalent bonding mechanism that corresponds to one-electron bonding 5 while the major contribution is electrostatic, as originally suggested by Foroutan-Nejad 4 .…”

Section: Introductionmentioning

confidence: 95%

Collective interactions among organometallics are exotic bonds hidden on lab shelves

et al. 2022

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Recent discovery of an unusual bond between Na and B in NaBH3− motivated us to look for potentially similar bonds, which remained unnoticed among systems isoelectronic with NaBH3−. Here, we report a novel family of collective interactions and a measure called exchange-correlation interaction collectivity index (ICIXC; $${ICI}\in \left[{{{{\mathrm{0,1}}}}}\right]$$ I C I ∈ 0, 1 ) to characterize the extent of collective versus pairwise bonding. Unlike conventional bonds in which ICIXC remains close to one, in collective interactions ICIXC may approach zero. We show that collective interactions are commonplace among widely used organometallics, as well as among boron and aluminum complexes with the general formula [Ma+AR3]b− (A: C, B or Al). In these species, the metal atom interacts more efficiently with the substituents (R) on the central atoms than the central atoms (A) upon forming efficient collective interactions. Furthermore, collective interactions were also found among fluorine atoms of XFn systems (X: B or C). Some of organolithium and organomagnesium species have the lowest ICIXC among the more than 100 studied systems revealing the fact that collective interactions are rather a rule than an exception among organometallic species.

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“…This is indeed what has been found when M′ is Mg but Anusiewicz et al observed for the interaction of Ca with AlH 3 or GaH 3 that the resulting neutral C 3 v complexes have values of θ that are significantly negative, typically on the order of −35°, so that the H atoms are instead directed toward M′; see Figure and Table . (Instead of this easily visualized “umbrella angle” θ, we could of course have specified these geometries in terms of the HMHH dihedral angle, in an analogous fashion to interesting previous work on stable anions of M′BH 3 systems …”

Section: Introductionmentioning

confidence: 99%

“…(Instead of this easily visualized "umbrella angle" θ, we could of course have specified these geometries in terms of the HMHH dihedral angle, in an analogous fashion to interesting previous work on stable anions of M′BH 3 systems. 7 ) Much of the specific interest in MgAlH 3 and CaAlH 3 has been derived from the fact that such molecules correspond to straightforward functionalizations of alane (AlH 3 ), which has numerous applications in organic synthesis as a reducing agent for specific functional groups, 8 and which is also used as a rocket fuel additive. 9 Theoretical research on MgAlH 3 and CaAlH 3 can be traced back to the late 1980s.…”

Section: ■ Introductionmentioning

confidence: 99%

Role of Dynamical Electron Correlation in the Differences in Bonding between CaAlH₃ and MgAlH₃

Penotti¹,

Karadakov

2021

J. Phys. Chem. A

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The most important factor behind the intriguing differences between the geometries of the M′AlH3 (M′ = Mg, Ca) molecules is shown to be dynamical electron correlation and not intramolecular Coulombic interactions, as previously thought. Spin-coupled generalized valence bond (SCGVB) calculations reveal the different bonding situations in the two molecules at their optimal geometries but do not explain why these geometries differ so much; the solution to this conundrum comes instead from detailed analysis of coupled-cluster (CCSD(T)) energies at model and optimal geometries.

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Attaching Be or Mg to BH3 results in the formation of BeBH3 and MgBH3 molecules capable of forming stable anions

Cited by 7 publications

References 46 publications

Unusual and Conventional Dative Bond Formation by s² Lone Pair Donation from Alkaline Earth Metal Atoms to BH₃, AlH₃, and GaH₃

Unusual and Conventional Dative Bond Formation by s² Lone Pair Donation from Alkaline Earth Metal Atoms to BH₃, AlH₃, and GaH₃

Collective interactions among organometallics are exotic bonds hidden on lab shelves

Role of Dynamical Electron Correlation in the Differences in Bonding between CaAlH₃ and MgAlH₃

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Attaching Be or Mg to BH3 results in the formation of BeBH3 and MgBH3 molecules capable of forming stable anions

Cited by 7 publications

References 46 publications

Unusual and Conventional Dative Bond Formation by s2 Lone Pair Donation from Alkaline Earth Metal Atoms to BH3, AlH3, and GaH3

Unusual and Conventional Dative Bond Formation by s2 Lone Pair Donation from Alkaline Earth Metal Atoms to BH3, AlH3, and GaH3

Collective interactions among organometallics are exotic bonds hidden on lab shelves

Role of Dynamical Electron Correlation in the Differences in Bonding between CaAlH3 and MgAlH3

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Unusual and Conventional Dative Bond Formation by s² Lone Pair Donation from Alkaline Earth Metal Atoms to BH₃, AlH₃, and GaH₃

Unusual and Conventional Dative Bond Formation by s² Lone Pair Donation from Alkaline Earth Metal Atoms to BH₃, AlH₃, and GaH₃

Role of Dynamical Electron Correlation in the Differences in Bonding between CaAlH₃ and MgAlH₃