Bonding analysis of planar hypercoordinate atoms via the generalized BLW‐LOL. Issue 26 (29th July 2013)

• Record Type: Journal Article
• Authors: Bomble, Laetitia; Steinmann, Stephan N.; Perez‐Peralta, Nancy; Merino, Gabriel; Corminboeuf, Clemence
• Is Part Of: Journal of computational chemistry. Volume 34:Issue 26(2013)
• Page Start: 2242
• Page End: 2248
• Publication Date: 2013-07-29
• Subjects: Chemistry -- Data processing -- Periodicals; 542.85
• DOI: 10.1002/jcc.23383
• Languages: English
• ISSNs: 0192-8651

Abstract

<abstract abstract-type="main"> <title> <x xml:space="preserve">Abstract</x> </title> <p>The multicenter bonding pattern of the intriguing hexa‐, hepta‐, and octacoordinate boron wheel series (e.g., <alternatives><inline-graphic mimetype="image" xlink:href="ark:/27927/pgg37402hc4" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /><mml:math display="inline" altimg="urn:x-wiley:01928651:media:jcc23383:jcc23383-math-0001" overflow="scroll" xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:mi mathvariant="normal">C</mml:mi><mml:msubsup><mml:mi mathvariant="normal">B</mml:mi><mml:mi mathvariant="normal">6</mml:mi><mml:mrow><mml:mi mathvariant="normal">2‐</mml:mi></mml:mrow></mml:msubsup></mml:mrow></mml:math></alternatives>, <alternatives><inline-graphic mimetype="image" xlink:href="ark:/27927/pgg37402hdp" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /><mml:math display="inline" altimg="urn:x-wiley:01928651:media:jcc23383:jcc23383-math-0002" overflow="scroll" xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:mi mathvariant="normal">C</mml:mi><mml:msubsup><mml:mi mathvariant="normal">B</mml:mi><mml:mi mathvariant="normal">7</mml:mi><mml:mi mathvariant="normal">‐</mml:mi></mml:msubsup></mml:mrow></mml:math></alternatives>, <alternatives><inline-graphic mimetype="image" xlink:href="ark:/27927/pgg37402h02" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /><mml:math display="inline" altimg="urn:x-wiley:01928651:media:jcc23383:jcc23383-math-0003" overflow="scroll" xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msubsup><mml:mi mathvariant="normal">B</mml:mi><mml:mi mathvariant="normal">8</mml:mi><mml:mrow><mml:mi mathvariant="normal">2‐</mml:mi></mml:mrow></mml:msubsup></mml:mrow></mml:math></alternatives>, and SiB<sub>8</sub> as well as the experimentally detected <alternatives><inline-graphic mimetype="image" xlink:href="ark:/27927/pgg37402h1m" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /><mml:math display="inline" altimg="urn:x-wiley:01928651:media:jcc23383:jcc23383-math-0004" overflow="scroll" xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:mi mathvariant="normal">C</mml:mi><mml:msubsup><mml:mi mathvariant="normal">B</mml:mi><mml:mi mathvariant="normal">7</mml:mi><mml:mi mathvariant="normal">‐</mml:mi></mml:msubsup></mml:mrow></mml:math></alternatives> isomer) is revised using the block‐localized wave function analyzed by the localized orbital locator (BLW‐LOL). The more general implementation of BLW combined with the LOL scalar field is not restricted to the analysis of the out‐of‐plane π‐system but can also provide an intuitive picture of the σ‐radial delocalization and of the role of the central atom. The results confirm the presence of a π‐ring current pattern similar to that of benzene. In addition, the LOL<sub>π</sub> isosurfaces along with the maximum intensity in the ΔLOL profiles located above and below the ring suggest that the central atom plays a minor role in the π‐delocalized bonding pattern. Finally, the analysis of the σ‐framework in these boron wheels is in line with a moderated inner cyclic rather than disk‐type delocalization. © 2013 Wiley Periodicals, Inc.</p> </abstract>