Characterization of the B⋯π-system interaction via topology of the experimental charge density distribution in the crystal of 3-chloro-7α-phenyl-3-borabicyclo[3.3.1]nonane

Lyssenko, Konstantin А.; Antipin, M. Yu.; Gurskii, M. E.; Bubnov, Yurii N.; Karionova, A. L.; Boese, Roland

doi:10.1016/j.cplett.2003.12.007

Cited by 23 publications

(17 citation statements)

References 28 publications

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“…One of the attractive features of AIM is its reliance on the charge density, a quantum mechanical observable, that is most often calculated but can, in principle, be measured via X-ray diffraction techniques [12][13][14][15]. In a similar fashion, the spin-polarized charge density is an observable that can be calculated or measured using spinpolarized neutron diffraction.…”

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confidence: 99%

“…Other studies have used bond path properties to offer first principles explanations of stress-induced failure in brittle and ductile alloys [7], as well as shear elastic constants in a variety of pure metals and alloys [8][9][10]. Building on these ideas and using the rigorous definitions of bond paths afforded by the theory, the anomalous behavior of iridium under shear was also explained [11].One of the attractive features of AIM is its reliance on the charge density, a quantum mechanical observable, that is most often calculated but can, in principle, be measured via X-ray diffraction techniques [12][13][14][15]. In a similar fashion, the spin-polarized charge density is an observable that can be calculated or measured using spinpolarized neutron diffraction.…”

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confidence: 99%

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Topology of the Spin-Polarized Charge Density in bcc and fcc Iron

2008

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We investigate the topology of the spin-polarized charge density in bcc and fcc iron. While the total spin-density is found to possess the topology of the non-magnetic prototypical structures, in some cases the spin-polarized densities are characterized by unique topologies; for example, the spin-polarized charge densities of bcc and high-spin fcc iron are atypical of any known for nonmagnetic materials. In these cases, the two spin-densities are correlated: the spin-minority electrons have directional bond paths with deep minima in the minority density, while the spin-majority electrons fill these holes, reducing bond directionality. The presence of two distinct spin topologies suggests that a well-known magnetic phase transition in iron can be fruitfully reexamined in light of these topological changes. We show that the two phase changes seen in fcc iron (paramagnetic to low-spin and low-spin to high-spin) are different. The former follows the Landau symmetrybreaking paradigm and proceeds without a topological transformation, while the latter also involves a topological catastrophe. Bader's topological theory of molecular structure, Atoms in Molecules (AIM), has been successfully applied to a variety of crystalline systems [1][2][3][4][5][6][7][8][9][10][11]. It has been employed to investigate the nature of bonding in materials ranging from high temperature alloys to biological systems. These have yielded surprising results, such as second neighbor bond paths in B2 ionic crystals [3] and transition metal aluminides [4], with the magnitude of the latter correlating to failure properties [5]. Other studies have used bond path properties to offer first principles explanations of stress-induced failure in brittle and ductile alloys [7], as well as shear elastic constants in a variety of pure metals and alloys [8][9][10]. Building on these ideas and using the rigorous definitions of bond paths afforded by the theory, the anomalous behavior of iridium under shear was also explained [11].One of the attractive features of AIM is its reliance on the charge density, a quantum mechanical observable, that is most often calculated but can, in principle, be measured via X-ray diffraction techniques [12][13][14][15]. In a similar fashion, the spin-polarized charge density is an observable that can be calculated or measured using spinpolarized neutron diffraction. Despite the information and insights that have come from topological investigations of the total charge density, the same analysis has yet to be performed on spin-polarized densities. Here, we report the results from the first such studies, exploring the spin-minority and spin-majority topologies of bodycentered-cubic (bcc) and face-centered-cubic (fcc) iron.This first application of AIM to spin-density sheds light on the origins of the magnetic phase transitions of fcc iron. It is argued that this system undergoes two distinct phase transitions during volume expansion: a second- * Electronic address: trjones@mines.edu order phase change, from a paramagnetic to a l...

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Topology of the Spin-Polarized Charge Density in bcc and fcc Iron

2008

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“…Analogous deviation of the boron atom from the substituent plane by 0.092(1) A ˚caused by 2p z /p-(Ph) dative interaction was shown to occur in 3-chloro-7a-phenyl-3-borabicyclo[3.3.1]nonane. 20 Reaction of Os 3 (l-H) 2 (CO) 10 (1) with B(CH 2 C(Me)QCH 2 ) 3 and B(CH 2 CHQCH 2 ) 3…”

Section: Resultsmentioning

confidence: 99%

Reactions of H2Os3(CO)10 with triallylboranes: formation of novel triosmium boron-containing olefin clusters

et al. 2009

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H 2 Os 3 (CO) 10 (1) reacts with triallylborane B(CH 2 CHQCH 2 ) 3 at 25 1C to form the cluster [Os 3 (CO) 10 (m-Z 2 :Z 2 -trans-MeHCQCH) 2 BC 3 H 7 ] (2). Reaction of 1 with a mixture of triallylboranetrimethallylborane (1 : 3) gives a mixture of clusters 2, [Os 3 (CO) (3) and {Os 3 (CO) 10 [m-Z 2 :Z 2 -(trans-MeCHQCH)(Me 2 CQCH)]BC 3 H 7 } (4). The reaction results in the B-C bond cleavage and the isomerization of two allyl fragments into substituted vinyl groups coordinated to the osmium atoms in an Z 2 -fashion, and reduction of the third fragment to a propyl group. The mechanism of the reaction is discussed based on isotope labelling and influence of the boron substituent ligand on the reaction path and product identity. Clusters 2, 3, 4 are characterized by spectroscopic means as well as by X-ray studies.

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“…The molecule of DTDABCN demonstrates an unusual stabilization of the cc conformation that can be attributed to the attractive S···S interaction, and the conformation preferences in the bicyclo[3.3.1]nonane system are particularly susceptible to weak intramolecular interactions. In particular, as it has been previously shown, the weak intramolecular B···π bonding can stabilize the extremely unusual chair–chair conformation of 7α-phenyl-3-borabicyclo[3.3.1]nonanes. , …”

Section: Introductionmentioning

confidence: 82%

“…In particular, as it has been previously shown, the weak intramolecular B 3 3 3 π bonding can stabilize the extremely unusual chairÀchair conformation of 7Rphenyl-3-borabicyclo[3.3.1]nonanes. 34,35 ' RESULTS AND DISCUSSION…”

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confidence: 99%

The “Hockey Sticks” Effect Revisited: The Conformational and Electronic Properties of 3,7-Dithia-1,5-diazabicyclo[3.3.1]nonane from the QTAIM Perspective

et al. 2011

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The conformational effects in bicyclo[3.3.1]nonanes, while thoroughly studied, have not yet received the full theoretical explanation. R. F. W. Bader's quantum theory of atoms in molecules presents unique opportunities for studying the stereoelectronic interactions (SEI) and weak intramolecular bonding leading to these effects. Here, we report the study of 3,7-dithia-1,5-diazabicyclo[3.3.1]nonane by means of the topological analysis of the calculated (MP2(full)/6-311++G**) and experimental (X-ray derived) charge density to reveal the origins of the so-called "hockey sticks" effect observed in similar compounds. A new explanation of the relative stability of bicyclo[3.3.1]nonane conformers based on the analysis of the QTAIM atomic energies is given. The H···H and S···S interactions in bicyclo[3.3.1]nonane and its dithia derivatives are shown to be significant factors contributing to the differences in the relative stability of the conformers.

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Characterization of the B⋯π-system interaction via topology of the experimental charge density distribution in the crystal of 3-chloro-7α-phenyl-3-borabicyclo[3.3.1]nonane

Cited by 23 publications

References 28 publications

Topology of the Spin-Polarized Charge Density in bcc and fcc Iron

Topology of the Spin-Polarized Charge Density in bcc and fcc Iron

Reactions of H2Os3(CO)10 with triallylboranes: formation of novel triosmium boron-containing olefin clusters

The “Hockey Sticks” Effect Revisited: The Conformational and Electronic Properties of 3,7-Dithia-1,5-diazabicyclo[3.3.1]nonane from the QTAIM Perspective

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