Hydrogen Bonding in Organometallic Crystals. 4. M−H- - -O Hydrogen-Bonding Interactions

Braga, Dario; Grepioni, Fabrizia; Tedesco, Emilio; Biradha, Kumar; Desiraju, Gautam R.

doi:10.1021/om9600250

Cited by 61 publications

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“…It is misleading to think that only the H⋅⋅⋅Y part constitutes the hydrogen bond. In a typical example that illustrates the interdependence of X, H, Y, and Z, a metal hydride MH is polarized sufficiently in the presence of an electronegative atom like oxygen in an OC fragment so that the H atom becomes protic and a hydrogen bond of the type M δ− H δ+ ⋅⋅⋅O δ− is formed 4a. It is a characteristic of complex systems that, in their totality, they are more than the sum of their constituents 4b.…”

Section: The Hydrogen Bondmentioning

confidence: 99%

A Bond by Any Other Name

2010

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bond theory · hydrogen bonds · solid-state structures · spectroscopy · structure elucidation The Hydrogen BondWhy are chemists and biologists still interested in hydrogen bonding? [1] The hydrogen bond X À H···Y À Z is an attractive interaction in which an electropositive H atom intercedes between two electronegative species X and Y and brings them closer together. The fundamental importance of the interaction follows from this particular role in molecular association. The hydrogen bond is strong enough to hold molecules such as XH and YZ together at normal temperatures and directional enough so that this association is orientationally specific. However, and depending on the nature of X and Y, it can also become weak enough to allow these molecules to come apart and directionless enough to permit loss of orientational specificity in the association of XH and YZ, more like a hydrophobic interaction. This chameleon-like nature of the interaction continues to baffle and excite the researcher.[2] Accordingly, the hydrogen bond plays a crucial role both in stabilizing static structures and in mediating dynamic processes. This is what accounts for its importance as a structure-defining element in supramolecular chemistry and as a major facilitator of biological reactions. [3] Depending on the nature of X, Y, and Z, the energy of a hydrogen bond lies in the range 0.5 to 40 kcal mol À1 . The strongest hydrogen bonds are stronger than the weakest of covalent bonds, while the weakest hydrogen bonds are practically indistinguishable, in energy terms, from van der Waals interactions. It is the intermediate energy range of many hydrogen bonds that makes them able to both associate and dissociate quickly at ambient temperatures-and it is this attribute that accounts for the importance of the hydrogen bond in mechanistic biology. All in all, it comes as no surprise that roughly one new paper on hydrogen bonding gets indexed in SciFinder every hour.The hydrogen bond is a complex interaction that has at least four chemical characteristics: electrostatics (acid/base); polarization (hard/soft); van der Waals (dispersion/repulsion); and covalency (charge transfer).[2k] It generally contains a minimum of four atoms, X, H, Y, and Z (or groups of atoms because a group of atoms can also constitute a valid acceptor fragment). The entire species XÀH···YÀZ is properly considered as the hydrogen bond because each part (XÀH, H···Y, and YÀZ) affects the other parts and is likewise affected by them. It is misleading to think that only the H···Y part constitutes the hydrogen bond. In a typical example that illustrates the interdependence of X, H, Y, and Z, a metal hydride M À H is polarized sufficiently in the presence of an electronegative atom like oxygen in an O=C fragment so that the H atom becomes protic and a hydrogen bond of the type M dÀ ÀH d+ ···O dÀ is formed. [4a] It is a characteristic of complex systems that, in their totality, they are more than the sum of their constituents.[4b] Accordingly, they are hard to define. In truth, e...

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Section: The Hydrogen Bondmentioning

confidence: 99%

A Bond by Any Other Name

2010

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“…Es ist irreführend, nur den Teil H⋅⋅⋅Y als Wasserstoffbrücke zu betrachten. Als ein typisches Beispiel, das die gegenseitige Abhängigkeit von X, H, Y und Z deutlich macht, mag ein Metallhydrid MH gelten, das durch die Anwesenheit eines elektronegativen Atoms, beispielsweise das Sauerstoffatom in einem OC‐Fragment, so stark polarisiert wird, dass das H‐Atom protisch wird und eine Wasserstoffbrücke des Typs M δ− H δ+ ⋅⋅⋅O δ− gebildet werden kann 4a. Ein Merkmal komplexer Systeme ist, dass sie in ihrer Gesamtheit mehr als die Summe ihrer Komponenten sind,4b und entsprechend schwer sind sie zu definieren.…”

Section: Die Wasserstoffbrückeunclassified

Die Wasserstoffbrücke – eine aktualisierte Definition

Desiraju

2010

Angewandte Chemie

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Warum beschäftigen sich Chemiker und Biologen immer noch mit Wasserstoffbrücken? [1] Die Wasserstoffbrücke X À H···Y À Z ist eine anziehende Wechselwirkung, bei der ein elektropositives H-Atom zwischen zwei elektronegativen Spezies X und Y angeordnet ist und sie einander näher bringt. Namen sind Schall und RauchAnscheinend werden Chemiker von Namen und Nomenklatur besonders fasziniert. In der Geschichte der Chemie gibt es unzählige Fälle von Diskussionen und Streit um Namen und Begriffe. So beschwerte sich Emil Fischer darüber, dass die Organiker seiner Zeit dem Harnstoff nicht den Status einer "organischen" Verbindung zusprechen wollten. Pauling und Ingold fochten um die Begriffe Resonanz und Mesomerie. "Resonanz" setzte sich durch -aber spielt dies aus heutiger Sicht wirklich eine Rolle? Eine "aromatische Verbindung" war ursprünglich eine Substanz mit einem angenehmen oder zumindest interessanten Geruch. Das Wort aromatisch wird auch heute noch in der Chemie verwendet, aber niemand käme auf die Idee, es mit Geruch in Verbindung zu bringen. Natürlich ist eine nichtaromatische Verbindung nicht etwa eine Verbindung ohne Geruch! Was also haben wir als Chemiker mit dem Begriff aromatisch gemacht? Im Wesentlichen haben wir ihn aus der Alltagssprache herausgelöst und in die chemische Fachsprache aufgenommen. Dabei ist er zu einem Trivialbegriff geworden, wie ja Chemiker für die häufige Verwendung von Trivialnamen für

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“…[27][28][29][30][31][32][33][34][35][36][37][38][39][40] Kryachko and Remacle 29 [41][42][43][44][45] and have also been investigated experimentally and theoretically by a number of research groups. [46][47][48][49][50][51][52] According to the criteria of X-H ••• M hydrogen bond suggested by Brammer et al, 44 the bridging hydrogen atom should be bonded to an electronegative element (X) and the metal atom (M) involved should be electron-rich. Gold is a late transition metal with a filled d shell.…”

Section: Introductionmentioning

confidence: 99%

Hydrogen bonds in the nucleobase-gold complexes: Photoelectron spectroscopy and density functional calculations

Cao

et al. 2012

The Journal of Chemical Physics

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The nucleobase-gold complexes were studied with anion photoelectron spectroscopy and density functional calculations. The vertical detachment energies of uracil-Au − , thymine-Au − , cytosine-Au − , adenine-Au − , and guanine-Au − were estimated to be 3.37 ± 0.08 eV, 3.40 ± 0.08 eV, 3.23 ± 0.08 eV, 3.28 ± 0.08 eV, and 3.43 ± 0.08 eV, respectively, based on their photoelectron spectra. The combination of photoelectron spectroscopy experiments and density functional calculations reveals the presence of two or more isomers for these nucleobase-gold complexes. The major isomers detected in the experiments probably are formed by Au anion with the canonical tautomers of the nucleobases. The gold anion essentially interacts with the nucleobases through N-H ••• Au hydrogen bonds.

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Hydrogen Bonding in Organometallic Crystals. 4. M−H- - -O Hydrogen-Bonding Interactions

Cited by 61 publications

References 61 publications

A Bond by Any Other Name

A Bond by Any Other Name

Die Wasserstoffbrücke – eine aktualisierte Definition

Hydrogen bonds in the nucleobase-gold complexes: Photoelectron spectroscopy and density functional calculations

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