An Unconventional Intermolecular Three‐Center N–H …︁ H2Re Hydrogen Bond in Crystalline [ReH5(PPh3)3]·indole·C6H6

Wessel, Jeremy; Lee, Jesse C.; Peris, Eduardo; Yap, Glenn P. A.; Fortin, Jeffrey B.; Ricci, John S.; Sini, Gjergji; Albinati, Alberto; Koetzle, Thomas F.; Eisenstein, Odile; Rheingold, Arnold L.; Crabtree, Robert H.

doi:10.1002/anie.199525071

Cited by 203 publications

(114 citation statements)

References 22 publications

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“…The N-H· · ·H 2 T-shaped arrangements were not discussed as possible types of hydrogen bond in the mentioned here study [105]. However such interactions were analyzed later since the more extended ab initio studies have been performed on XH 4 cluster. The decomposition of the energy of interaction performed within the variationperturbation approach [67,68] for the XH + 4 · · ·H 2 systems shows that the delocalization term is the most important attractive one followed by the electrostatic and dispersion contributions [106].…”

Section: The A-h· · ·σ Interactions: From Complexes To Clustersmentioning

confidence: 93%

“…In the article mentioned above [1] and other early studies of Crabtree and coworkers [4,5] the dihydrogen bond (DHB) term was reserved for O-H· · ·H-M and N-H· · ·H-M interactions (where M designates the transition metal or boron) but the authors have claimed that possible elements connected with the hydridic hydrogen are¨currently known as boron and the transition metals; other cases will no doubt be discovered in the future [6].¨And really further studies have shown that numerous other interactions can be classified as DHBs [7], even C-H· · ·H-C contacts were considered as the interactions of this type [8,9]. It was also found that for numerous H· · ·H links the energy of interaction exceeds 10 or even 20 kcal/mol [10][11][12][13][14][15][16].…”

Section: Introductionmentioning

confidence: 94%

“…Even in cases of the BH Ab initio calculations on intermolecular and intramolecular DHBs for Mo, W, Ru, Re and Ir complexes have been carried out showing the H· · · H interaction energy greater than 5 kcal/mol and sometimes greater than 10 kcal/mol [12][13][14], similarly as for strong conventional O-H· · · O and N-H· · · O hydrogen bonds. There are other early theoretical studies on dihydrogen bonded systems, for example the calculations (MP2, MP4, QCISD(T) and B3LYP methods) were performed on the dihydrogen bonded complexes between the hydrides LiH, NaH, BeH 2 , MgH 2 , CH 4 , SiH 4 , GeH 4 , SnH 4 and hydrofluoric acid and the correlations between H· · ·H distance and the binding energy were presented [58,59].…”

Section: First Theoretical Calculations On the Dihydrogen Bondmentioning

confidence: 99%

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What is Common for Dihydrogen Bond and H…σ Interaction—Theoretical Analysis and Experimental Evidences

Grabowski

2015

Challenges and Advances in Computational Chemistry and Physics

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Two types of the hydrogen bond are described and compared here; the A-H· · ·H-B dihydrogen bond and the A-H· · ·σ interaction. In a case of the dihydrogen bond the H· · ·H contact between the hydrogen atoms characterized by the opposite charges is observed; i.e. between the protonic (A)H and hydridic (B)H hydrogens. For the A-H· · ·σ hydrogen bond the A-H proton donating bond interacts with the σ-electrons of the molecular hydrogen. These interactions are topologically different since for DHB the bond path linking the attractors of H-atoms with the corresponding bond critical point is observed. For the A-H· · ·σ interaction the bond path between the (A)H-atom attractor and the bond critical point of the H-H bond of the molecular hydrogen is observed. Both types of the hydrogen bond are characterized by the significant σ → σ* orbital-orbital interaction, σ BH → σ AH * in a case of DHB and σ HH → σ AH * for A-H· · ·σ. There are also evidences that A-H· · ·H-B and A-H· · ·σ may be classified as the hydrogen bonds. The examples of complexes characterized by the mentioned above types of the hydrogen bond are analyzed in this chapter, the theoretical as well as experimental examples are presented. IntroductionIt was 20 years ago when R. H. Crabtree and coworkers noted that¨Typical hydrogen bond acceptors possess an O or N lone pair, but more recently, the σ-electron pair of a transition metal hydride has been shown to give intramolecular N-H· · ·H-M and O-H· · ·H-M hydrogen bonds of an unconventional type, for which we suggest the term dihydrogen bonds. These interactions have bond strengths of 4-6 kcal/mol and H· · ·H distances of ca. 1.7-1.9 Å and seem to play a role in proton transfer, fluxional processes and other reactions [1]. The authors also wrote in the footnote of the article that¨a referee points out that these unconventional hydrogen bonds require a

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Section: The A-h· · ·σ Interactions: From Complexes To Clustersmentioning

confidence: 93%

Section: Introductionmentioning

confidence: 94%

Section: First Theoretical Calculations On the Dihydrogen Bondmentioning

confidence: 99%

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What is Common for Dihydrogen Bond and H…σ Interaction—Theoretical Analysis and Experimental Evidences

Grabowski

2015

Challenges and Advances in Computational Chemistry and Physics

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“…Hydrogen bonds can be classified as weak, moderate and strong, depending upon their energies [7]. Hydrogen bonds can also express unique features that allow them to be classified as blue-shifted hydrogen bonds and dihydrogen bonds [8][9][10][11]. In blue-shifted hydrogen bonds, the stretching vibration frequencies associated with CH or NH vibrations are blue-shifted with respect to the corresponding isolated species after hydrogen bond formation.…”

Section: Introductionmentioning

confidence: 99%

Electronic‐Excited‐State Structures and Properties of Hydrated DNA Bases and Base Pairs

Shukla¹,

Leszczyński²

2010

Hydrogen Bonding and Transfer in the Excited State

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Computational chemistry methods have been established as an attractive and reliable alternative to the costly and time-consuming experiments used to determine structures, properties and reactivities of molecular species. Although the modelling of the exact environmental conditions at the high theoretical level is still very expensive and may not be possible in several cases, computational methods are capable of providing reliable predictions in many ways, which can be useful to experimentalists and to the general scientific community [1,2]. Theoretical methods are especially attractive in areas such as the determination of excitedstate geometries of complex molecules, where experiments are not yet possible. Another example of the role of computational studies is the quantitative prediction of amino group pyramidalization of nucleic acid bases. The neutron diffraction study of adenine crystals has suggested a non-planar amino group [3]. Using the ab initio quantum chemical method, the amino groups of bases were suggested to be non-planar more than a decade ago [4,5]. However, only recently, an experimental method has verified such non-planarity in the gas phase of adenine and cytosine, using the measurement of the vibrational transition moment angles [6]. We strongly believe that theoretical and experimental methods are complementary to each other, and a judicious decision is needed for their efficient applications to determine the structures and properties of different systems.Hydrogen bonding is ubiquitous. It plays an important role in different aspects of all living organisms. Hydrogen bonds can be classified as weak, moderate and strong, depending upon their energies [7]. Hydrogen

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“…Through the X-rays diffraction analysis, the Crabtree's research group 6 has shown that DHB complexes are formed by proton donors (H +δ ) and hydride compounds (H -δ ) [7][8] . On the other hand, by considering the formation of the N-H +δ ···H -δ -Y DHB complex, where normally N is an electronegative group and Y is a alkali metal (AM) or alkali earth metals (AEM) [9][10][11][12][13][14] , some theoretical investigations documented by Grabowski 15 has revealed the existence of H +δ ···H -δ -Y DHB complexes formed by Lithium, Sodium, Magnesium, and a different proton acceptor: the methane. Furthermore, it was also verified that the F-H +δ ···H -δ -CH 3 DHB complex is formed through the interaction of the methane with hydrofluoric acid.…”

Section: Introductionmentioning

confidence: 99%

Improper Hydrogen Bonds - A Theoretical Study About the Molecular Structure of Intermolecular Systems Formed by H3c-H+δ...x and H3c+δ...h-Y With X = Cl- Or F- And Y = Cl or F

Oliveira

2009

J. Chil. Chem. Soc.

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In this work is presented a theoretical study of the molecular properties of the H 3 C-H···X and H 3 C +δ ···H-Y intermolecular systems with X = Cl -or F -and Y = Cl or F. In the H 3 C-H···X complex, it is formed a traditional hydrogen bond between the Cl -or F -anions and the hydrogen atom of the methyl. About the H 3 C +δ ···H-Y complex, it was observed an improper hydrogen bond because the carbon atom of the methyl cation function as a proton acceptor. In this insight, the capacity of methane to interact with halogen anions (Cl -or F -) and molecular acids (HCl or HF) was examined at the B3LYP/6-311++G(3df,3dp) level of calculation. Moreover, the interaction strengths of the H 3 C-H···X and H 3 C +δ ···H-Y complexes was evaluated by computing their intermolecular distances and binding energies. Finally, QTAIM calculations also were executed with the purpose to examine the intermolecular interactions through the quantification of their electronic densities (ρ) as well as by the interpretation of the Laplacian operators (∇ 2 ρ).

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An Unconventional Intermolecular Three‐Center N–H …︁ H₂Re Hydrogen Bond in Crystalline [ReH₅(PPh₃)₃]·indole·C₆H₆

Cited by 203 publications

References 22 publications

What is Common for Dihydrogen Bond and H…σ Interaction—Theoretical Analysis and Experimental Evidences

What is Common for Dihydrogen Bond and H…σ Interaction—Theoretical Analysis and Experimental Evidences

Electronic‐Excited‐State Structures and Properties of Hydrated DNA Bases and Base Pairs

Improper Hydrogen Bonds - A Theoretical Study About the Molecular Structure of Intermolecular Systems Formed by H3c-H+δ...x and H3c+δ...h-Y With X = Cl- Or F- And Y = Cl or F

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