Accurate single crystal and gas-phase molecular structures of acenaphthene: a starting point in the search for the longest C–C bond

Vishnevskiy, Yury V.; Otlyotov, Arseniy A.; Lamm, Jan‐Hendrik; Stammler, Georg; Girichev, G. V.; Mitzel, Norbert W.

doi:10.1039/d2cp05613e

Cited by 6 publications

(13 citation statements)

References 85 publications

(105 reference statements)

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“…Notably, this results in a handful of penta-coordinated Ge compounds obtained having TBP geometry which are uncommon in Ge chemistry. 11 d The viable expansion of the peri -distances 22 in the two intramolecular P–Ge bonds in 3 iPr and 3 Ph allows smooth structural rearrangements with the addition of nucleophiles.…”

Section: Resultsmentioning

confidence: 99%

“…Contemporary research in the field of main-group Lewis acids 17 has introduced the concepts of geometrically constrained Lewis acids, 18 main group Lewis acid/ligand assisted cooperative bond activation, 19 hidden frustrated Lewis pair (FLP) chemistry 20 in intra-molecular Lewis base stabilized Lewis acidic fragments. 21 Taking advantage of the enforced proximity in peri -substituted acenaphthenes, 22 herein we have established the unprecedented intramolecularly phosphine-stabilized tetra-coordinated di-cationic Ge( iv ) compounds. The aptitude of these geometrically constrained Ge( iv ) di-cationic species as Lewis acids has been assessed based on experimental findings and computational analyses.…”

Section: Introductionmentioning

confidence: 99%

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Intramolecular donor-stabilized tetra-coordinated germanium(iv) di-cations and their Lewis acidic properties

Peddi,

Khan,

Gonnade

et al. 2023

Chem. Sci.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Intramolecular donor-stabilized tetra-coordinated germanium(iv) di-cations and their Lewis acidic properties

Peddi,

Khan,

Gonnade

et al. 2023

Chem. Sci.

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“…Many theoretical and experimental studies show pronounced deviations from the "normal" C(sp 3 )À C(sp 3 ) bond distance of 1.54 Å in ethane, and in many cases interactions between substituents change this value significantly (for the latest statistical analysis, see [2] ). The experimentally observed CÀ C bond shortening reaches 1.436(3) Å [3] for the trimethylsilylated tetrahedrane dimer (1) and computations predict up to 1.313 Å for some compressed cage hydrocarbons, such as hypothetical [4] bridged tetrahedryl-tetrahedrane (2) (Figure 1).…”

Section: Discussionmentioning

confidence: 99%

Long but Strong C−C Single Bonds: Challenges for Theory

Fokin

2023

The Chemical Record

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Theoretical challenges in describing molecules with anomalously long single C−C bonds are analyzed in terms of the relative contributions of stabilizing and destabilizing intramolecular interactions. Diamondoid dimers that are stable despite the presence of C−C bonds up to 1.7 Å long, as well as other bulky molecules stabilized due to intramolecular noncovalent interactions (London dispersions) are discussed. The unexpected stability of highly crowded molecules, such as diamondoid dimers and tert‐butyl‐substituted hexaphenylethanes, calls for reconsideration of the “steric effect” traditionally thought to destabilize the molecule. Alternatively, “steric attraction” helps to understand bonding in sterically overloaded molecules, whose structural and energetic analysis requires a proper theoretical description of noncovalent interactions.

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“…We studied acenaphthene (Scheme : C ) by GED, XRD, and high-level QC calculations . All methods show that acenaphthene molecules are planar and possess a nontwisted ethylene bridge.…”

Section: Alkyl–alkyl Interactionsmentioning

confidence: 99%

“…We studied acenaphthene (Scheme 4: C) by GED, XRD, and high-level QC calculations. 39 All methods show that acenaphthene molecules are planar and possess a nontwisted ethylene bridge. The aliphatic C−C bond length is the same in the gas [1.560(4) Å] and the solid phase [1.5640( 4) Å] within experimental uncertainty.…”

Section: Lists Values For the Central C−c Bond Lengths As Determined ...mentioning

confidence: 99%

Phase-Dependence of Molecular Structures Arising from Weak London Dispersion Interactions

Mitzel,

Lamm

2023

Acc. Chem. Res.

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Conspectus The structures of molecules can be different in different phases. Intermolecular forces, even those of weak noncovalent interactions (WNCIs), can lead to a preference for quite different conformations in the solid, the gas, and the liquid phases. WNCIs can cause variations in bond lengths, angles, and torsional angles. Since structure is a fundamental concept in chemistry, the knowledge of structural changes with phase is important to understand the source and effects of distorting contributions from WNCIs but also as a predictive tool for the design and stabilization of new bonding situations. X-ray crystallography is ubiquitous and now mostly straightforward to perform, but facilities for the determination of accurate gas-phase structure determination are rare, and gas-phase work is laborious and time-consuming. There are currently about 1.25 million crystal structures and more than 12 500 experimental gas-phase structures, but the intersection of the two data sets that can tell us about the structural differences of the same molecule in different phases is surprisingly small. In this Account, we describe several cases of WNCI-dominated systems for which accurate experimental structure determinations exist for both the gas phase and the solid state and, in one case, also for solution. The examples include aryl–aryl, aryl–alkyl, and alkyl–alkyl interactions; systems with chalcogen and halogen bonding; and fluorine-based interactions in arylboranes. We work out the role of WNCIs in stabilizing large, strained, or sterically overloaded molecules. We will show how flexible molecules will fold under the action of WNCIs when isolated in the gas and how they fold or unfold when they are embedded in an environment of neighbors in crystals. We will show how they can vary in strength when the substitution patterns in aryl groups are changed by different halogens and how intramolecular WNCIs, such as those forming rings, change when such systems experience additional intermolecular WNCIs. Overall, we hope that this Account will give the reader an idea of the type and magnitude of structural changes that can be expected from a free molecule in the gas phase or a single molecule calculated by quantum chemistry compared with one embedded in a crystal. This should define the limits of comparability and provide some predictive concepts of the distortions and variations to be expected.

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Accurate single crystal and gas-phase molecular structures of acenaphthene: a starting point in the search for the longest C–C bond

Abstract: The molecular structure of acenaphthene has been determined experimentally in the gas phase using gas electron diffraction intensities and literature-available rotational constants. Supplementary highlevel quantum-chemical calculations were utilized in refinements...

Cited by 6 publications

References 85 publications

Intramolecular donor-stabilized tetra-coordinated germanium(iv) di-cations and their Lewis acidic properties

Intramolecular donor-stabilized tetra-coordinated germanium(iv) di-cations and their Lewis acidic properties

Long but Strong C−C Single Bonds: Challenges for Theory

Phase-Dependence of Molecular Structures Arising from Weak London Dispersion Interactions

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