Dative or Not Dative?

Himmel, Daniel; Krossing, Ingo; Schnepf, Andreas

doi:10.1002/anie.201403078

Cited by 163 publications

(98 citation statements)

References 8 publications

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“…have been used to describe structures involving main-group compounds. [28] In a very recent essay entitled: "Chemistry: A Panoply of Arrows," Prof.…”

Section: Reaction Mechanismmentioning

confidence: 99%

Unraveling reaction mechanisms by means of Quantum Chemical Topology Analysis

Andrés

González-Navarrete

Safont

2014

Int J of Quantum Chemistry

100

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A chemical reaction can be understood in terms of geometrical changes of the molecular structures and reordering of the electronic densities involved in the process; therefore, identifying structural and electronic density changes taking place along the reaction coordinate renders valuable information on reaction mechanism. Understanding the atomic rearrangements that occur during chemical reactions is of great importance, and this perspective aims to highlight the major developments in quantum chemical topology analysis, based on the combination of electron localization function and catastrophe theory as useful tools in elucidating the bonding and reactivity patterns of molecules. It reveals all the expected, but still ambiguous, elements of electronic structure extensively used by chemists. The chemical bonds determine chemical reactivity, and this technique offers the possibility of their visualization, allowing chemists to understand how atoms bond, how and where bonds are broken/ formed along a given reaction pathway at a most fundamental level, and so, better following and understanding the changes in the bond pattern. Their results clearly herald a new era, in which the atomic imaging of chemical bonds will constitute a new method for examining chemical structures and reaction mechanisms. The important feature of this procedure is that in practice the scope of its values is systemindependent. In addition, from a practical point of view, it is cheap to calculate and implement because wave functions are the required input, which are easily available from standard calculations. To capture these results two reaction mechanisms: isomerization of C(BH) 2 carbene and the thermal cycloheptatriene-norcaradiene isomerizations have been selected, indicating both the generality and utility of this type of analysis.

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“…have been used to describe structures involving main-group compounds. [28] In a very recent essay entitled: "Chemistry: A Panoply of Arrows," Prof.…”

Section: Reaction Mechanismmentioning

confidence: 99%

Unraveling reaction mechanisms by means of Quantum Chemical Topology Analysis

Andrés

González-Navarrete

Safont

2014

Int J of Quantum Chemistry

100

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“…In a similar manner, the synthesis of twofold base adducts of monovalent boron extended this concept to elements beyond carbon 21-24 , and more recently analogous '-ones' of heavier group 14 elements have also been realized 25 . This rethinking of the bonding in main-group compounds in terms of bonding between a Lewis donor and a Lewis acceptor has recently spurred heated debate in the literature [26][27][28] .While earlier reports on carbon suboxide and its cationic nitrogen analogue presume a cumulenic (O 5 C 5 E 5 C 5 O) (where E is C or N) structure 9,10 , Frenking and co-workers have suggested that these compounds might be better considered as Lewis adducts (OCRErCO). In contrast, they predicted that the hypothetical borylene dicarbonyl HB(CO) 2 would contain much more ERCO p backbonding than in the carbon and nitrogen dicarbonyls (when E is boron, p backbonding is 33.8% of the total bonding energy, whereas it is 5.2% and 10.0% for nitrogen and carbon, respectively) 20 , making the boron analogue much more akin to transition-metal bis(CO) counterparts.…”

mentioning

confidence: 99%

“…In a similar manner, the synthesis of twofold base adducts of monovalent boron extended this concept to elements beyond carbon [21][22][23][24] , and more recently analogous '-ones' of heavier group 14 elements have also been realized 25 . This rethinking of the bonding in main-group compounds in terms of bonding between a Lewis donor and a Lewis acceptor has recently spurred heated debate in the literature [26][27][28] .…”

mentioning

confidence: 99%

“…After removal of molybdenum hexacarbonyl by fractional crystallization from toluene, blue crystals were obtained (compound 2, see Fig. 1; note that the monovalent boron compounds 2-4 and 8 are depicted in both conventional covalent forms and Lewis donor/acceptor forms in this figure, according to the conflicting ideas set out in the aforementioned debate on the existence of dative bonds in main-group compounds [26][27][28]. This compound showed a strongly upfield-shifted 11 B nuclear magnetic resonance (NMR) signal (d -32.2) compared to that of the precursor 1b (d 155) and signals corresponding to the Tp fragment in the 1 H NMR spectrum.…”

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confidence: 99%

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Multiple complexation of CO and related ligands to a main-group element

Braunschweig

Dewhurst

Hupp

et al. 2015

Nature

306

214

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The ability of an atom or molecular fragment to bind multiple carbon monoxide (CO) molecules to form multicarbonyl adducts is a fundamental trait of transition metals. Transition-metal carbonyl complexes are vital to industry, appear naturally in the active sites of a number of enzymes (such as hydrogenases), are promising therapeutic agents, and have even been observed in interstellar dust clouds. Despite the wealth of established transition-metal multicarbonyl complexes, no elements outside groups 4 to 12 of the periodic table have yet been shown to react directly with two or more CO units to form stable multicarbonyl adducts. Here we present the synthesis of a borylene dicarbonyl complex, the first multicarbonyl complex of a main-group element prepared using CO. The compound is additionally stable towards ambient air and moisture. The synthetic strategy used--liberation of a borylene ligand from a transition metal using donor ligands--is broadly applicable, leading to a number of unprecedented monovalent boron species with different Lewis basic groups. The similarity of these compounds to conventional transition-metal carbonyl complexes is demonstrated by photolytic liberation of CO and subsequent intramolecular carbon-carbon bond activation.

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“…The bonding in compound 2a can be described using either zwitterionic (2a) or dative forms (2a') (Scheme 4). Neither model is completely accurate and the debate over which is more appropriate can be a contentious issue [25,26] which we will not delve into here. For the sake of consistency, we will by default refer to and draw the compound as the arsino-phosphonium form, 2a, unless the phosphino-arsenium form is to be discussed specifically.…”

Section: Synthesis Of Arsanylidene-phosphorane 3amentioning

confidence: 98%

Hydride Abstraction and Deprotonation – an Efficient Route to Low Coordinate Phosphorus and Arsenic Species

et al. 2015

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Treatment of Acenap(PiPr 2 )(EH 2 ) (Acenap = acenaphthene-5,6-diyl; 1a, E = As; 1b, E = P) with Ph 3 C·BF 4 resulted in hydride abstraction to give [Acenap(PiPr 2 )(EH)][BF 4 ] (2a, E = As; 2b, E = P). These represent the first structurally characterised phosphino/arsino-phosphonium salts with secondary arsine/phosphine groups, as well as the first example of a Lewis base stabilised primary arsenium cation. Compounds 2a and 2b were deprotonated with NaH to afford low co-ordinate species Acenap(PiPr 2 )(E) (3a, E = As; 3b, E = P). This provides an alternative and practical synthetic pathway to the phosphanylidene-σ 4 -phosphorane 3b and provides mechanistic insight into the formation of arsanylidene-σ 4 -phosphorane 3a, indirectly supporting the hypothesis that the previously reported dehydrogenation of 1a occurs via an ionic mechanism.

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Dative or Not Dative?

Abstract: Is a meatball an animal praline? The authors of the Essay Dative Bonds in Main‐Group Compounds: A Case for Fewer Arrows! respond to the criticism of Gernot Frenking and correct one point in their original Essay.

Cited by 163 publications

References 8 publications

Unraveling reaction mechanisms by means of Quantum Chemical Topology Analysis

Unraveling reaction mechanisms by means of Quantum Chemical Topology Analysis

Multiple complexation of CO and related ligands to a main-group element

Hydride Abstraction and Deprotonation – an Efficient Route to Low Coordinate Phosphorus and Arsenic Species

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