Cr−Cr Quintuple Bonds: Ligand Topology and Interplay Between Metal−Metal and Metal−Ligand Bonding
| Author(s) | Falceto, Andrés | |
| Author(s) | Theopold, Klaus H. | |
| Author(s) | Alvarez, Santiago | |
| Ordered Author | Andrés Falceto, Klaus H. Theopold, and Santiago Alvarez | |
| UD Author | Theopold, Klaus H. | en_US |
| Date Accessioned | 2015-12-16T19:37:42Z | |
| Date Available | 2015-12-16T19:37:42Z | |
| Copyright Date | Copyright © 2015 American Chemical Society | en_US |
| Publication Date | 2015-10-26 | |
| Description | Publisher's PDF. | en_US |
| Abstract | Chromium–chromium quintuple bonds seem to be approaching the lower limit for their bond distances, and this computational density functional theory study tries to explore the geometrical and electronic factors that determine that distance and to find ways to fine-tune it via the ligand choice. While for monodentate ligands the Cr–Cr distance is predicted to shorten as the Cr–Cr–L bond angle increases, with bridging bidentate ligands the trend is the opposite, since those ligands with a larger number of spacers between the donor atoms favor larger bond angles and longer bond distances. Compared to Cr–Cr quadruple bonds, the quintuple bonding in Cr2L2 compounds (with L a bridging bidentate N-donor ligand) involves a sophisticated mechanism that comprises a positive pyramidality effect for the σ and one π bond, but a negative effect for one of the δ bonds. Moreover, the shorter Cr–Cr distances produce a mismatch of the bridging ligand lone pairs and the metal acceptor orbitals, which results in a negative correlation of the Cr–Cr and Cr–N bond distances in both experimental and calculated structures. | en_US |
| Department | University of Delaware. Center for Catalytic Science & Technology. | en_US |
| Citation | Cr–Cr Quintuple Bonds: Ligand Topology and Interplay Between Metal–Metal and Metal–Ligand Bonding. - Inorg Chem. (- 22):- 10966. | en_US |
| DOI | doi:10.1021/acs.inorgchem.5b02059 | en_US |
| ISSN | 0020-1669 ; e-1520-510X | en_US |
| URL | http://udspace.udel.edu/handle/19716/17324 | |
| Language | en_US | en_US |
| Publisher | American Chemical Society | en_US |
| dc.rights | ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. | en_US |
| dc.source | Inorganic Chemistry | en_US |
| dc.source.uri | http://pubs.acs.org/journal/inocaj | en_US |
| Title | Cr−Cr Quintuple Bonds: Ligand Topology and Interplay Between Metal−Metal and Metal−Ligand Bonding | en_US |
| Type | Article | en_US |
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