Homopolar dihydrogen bonding in main group hydrides: discovery, consequences, and applications

Wolstenholme, David J.; Dobson, Jessica L.; McGrady, G. Sean

doi:10.1039/c5dt00221d

Cited by 50 publications

(43 citation statements)

References 90 publications

(152 reference statements)

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“…Our conclusions are fully in line with the other, mostly experimental studies, in which the destabilizing role of BH¨¨¨HB interactions were also suggested [68][69][70][71][72]. McGrady and coworkers reported the opposite in their series of recent articles [17,20,21,29]. Due to the fact that such interactions are clearly a matter of debate, in addition, we performed the Interacting Quatum Atoms (IQA) based study for the tetrameric models of LiNMe 2 BH 3 .…”

Section: Resultssupporting

confidence: 71%

“…It has been demonstrated that the former feature of ammonia borane crystal originates predominantly from the existence of polar dihydrogen bonds N-H δ`¨¨¨´δ H-B between monomers [11][12][13][14][15][16]. Furthermore, it has been proven that the presence of N-H δ`¨¨¨´δ H-B as well as other non-covalent interactions not only determines the stability, but it can also facilitate various steps of dehydrogenation [5][6][7][8][11][12][13][14][15][16][17][18][19][20][21][22][23].…”

Section: Introductionmentioning

confidence: 99%

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Non-Covalent Interactions in Hydrogen Storage Materials LiN(CH3)2BH3 and KN(CH3)2BH3

2016

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Abstract:In the present work, an in-depth, qualitative and quantitative description of non-covalent interactions in the hydrogen storage materials LiN(CH 3 ) 2 BH 3 and KN(CH 3 ) 2 BH 3 was performed by means of the charge and energy decomposition method (ETS-NOCV) as well as the Interacting Quantum Atoms (IQA) approach. It was determined that both crystals are stabilized by electrostatically dominated intra-and intermolecular M¨¨¨H-B interactions (M = Li, K). For LiN(CH 3 ) 2 BH 3 the intramolecular charge transfer appeared (B-HÑLi) to be more pronounced compared with the corresponding intermolecular contribution. We clarified for the first time, based on the ETS-NOCV and IQA methods, that homopolar BH¨¨¨HB interactions in LiN(CH 3 ) 2 BH 3 can be considered as destabilizing (due to the dominance of repulsion caused by negatively charged borane units), despite the fact that some charge delocalization within BH¨¨¨HB contacts is enforced (which explains H¨¨¨H bond critical points found from the QTAIM method). Interestingly, quite similar (to BH¨¨¨HB) intermolecular homopolar dihydrogen bonds CH¨¨¨HC appared to significantly stabilize both crystals-the ETS-NOCV scheme allowed us to conclude that CH¨¨¨HC interactions are dispersion dominated, however, the electrostatic and σ/σ*(C-H) charge transfer contributions are also important. These interactions appeared to be more pronounced in KN(CH 3 ) 2 BH 3 compared with LiN(CH 3 ) 2 BH 3 .

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Section: Resultssupporting

confidence: 71%

Section: Introductionmentioning

confidence: 99%

Non-Covalent Interactions in Hydrogen Storage Materials LiN(CH3)2BH3 and KN(CH3)2BH3

2016

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“…Thel ack of BCPs between the outer hydrides can be attributed to the much larger H outer ···H outer distances (Table 1) and is in agreement with the absence of strong magnetic coupling between these hydrides.T he considerable electron density along the H outer ···H center bond paths suggests that such counterintuitive hydride···hydride interactions may be afirst step to hydrogen formation:H À + H À ! [34] As solids,the Ca and Sr hydride clusters decompose at atemperature of 135 8 8C. [34] As solids,the Ca and Sr hydride clusters decompose at atemperature of 135 8 8C.…”

Section: Zuschriftenmentioning

confidence: 99%

A Simple Route to Calcium and Strontium Hydride Clusters

et al. 2017

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The first strontium hydride complex has been obtained by simply treating Sr[N(SiMe 3 ) 2 ] 2 with PhSiH 3 in the presence of PMDTA. The Sr complex Sr 6 H 9 [N(SiMe 3 ) 2 ] 3 ·-(PMDTA) 3 crystallizes as an "inverse cryptand": an interstitial H À is surrounded by aSr 6 H 8 4+ cage decorated with amide and PMDTAl igands.T he analogous Ca complex could also be obtained and both retain their solid-state structures in solution: 1 HNMR spectra in C 6 D 6 show two doublets and one nonet (4:4:1). Up to 90 8 8C, no coalescence is observed. The Ca cluster was investigated by DFT calculations and shows atypically low charges on Ca (+ 1.14) and H( À0.59) whichs ignifies an unexpectedly lowi onicity.A IM analysis shows hydride···hydride bond paths with considerable electron densities in the bond critical point. The clusters thermally decompose into larger,undefined, metal hydride aggregates.

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“…Significant hydride-hydride interactions including bond paths with bond critical points have been found for the solid-state structure of LiH, but not for NaH. [20,21] Theoretical studies on the decomposition of the rhombic dimers (MH) 2 , M ¼ Li, Na, K, into the elements revealed a more facile H 2 formation for Na and K compared with Li, due to the larger size and poorer orbital overlap with hydrogen for the heavier ions. [20,22] This qualitative trend is in line with the observed decomposition temperatures of the alkali metal hydrides; see Table 1.…”

Section: Introductionmentioning

confidence: 99%

“…[20,21] Theoretical studies on the decomposition of the rhombic dimers (MH) 2 , M ¼ Li, Na, K, into the elements revealed a more facile H 2 formation for Na and K compared with Li, due to the larger size and poorer orbital overlap with hydrogen for the heavier ions. [20,22] This qualitative trend is in line with the observed decomposition temperatures of the alkali metal hydrides; see Table 1. Problematic is the high temperature required for hydrogen release in these lighter hydrides (see Table 1), which is in part a result of the high lattice energies of the lighter MH phases, plus the reversibility of this reaction.…”

Section: Introductionmentioning

confidence: 99%

Alkali Metal Hydride Complexes: Well-Defined Molecular Species of Saline Hydrides

Fohlmeister

Stasch

2015

Aust. J. Chem.

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The first examples of well-defined alkali metal hydride complexes have been synthesised and characterised in recent years, and their properties and underlying principles for their generation and stabilisation are emerging. This article gives an account of the hydrides of the alkali metals (Group 1 metals) and selected '-ate' complexes containing hydrides and alkali metals, and reviews the chemistry of well-defined alkali metal hydride complexes including their syntheses, structures, and characteristics. The properties of the alkali metal hydrides LiH, NaH, KH, RbH, and CsH are dominated by their ionic NaCl structure. Stable, soluble, and well-defined LiH and NaH complexes have been obtained by metathesis and b-hydride elimination reactions that require suitable ligands with some steric bulk and the ability to coordinate to several metal ions. These novel hydride complexes reward with higher reactivity and different properties compared with their parent ionic solids.

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Homopolar dihydrogen bonding in main group hydrides: discovery, consequences, and applications

Cited by 50 publications

References 90 publications

Non-Covalent Interactions in Hydrogen Storage Materials LiN(CH3)2BH3 and KN(CH3)2BH3

Non-Covalent Interactions in Hydrogen Storage Materials LiN(CH3)2BH3 and KN(CH3)2BH3

A Simple Route to Calcium and Strontium Hydride Clusters

Alkali Metal Hydride Complexes: Well-Defined Molecular Species of Saline Hydrides

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