Exploring the forces that control the P-C bond length in phosphamides and their complexes: The key role of hyperconjugation
| dc.contributor.author | Tsipis, A. C. | en |
| dc.date.accessioned | 2015-11-24T16:58:18Z | |
| dc.date.available | 2015-11-24T16:58:18Z | |
| dc.identifier.issn | 0276-7333 | - |
| dc.identifier.uri | https://olympias.lib.uoi.gr/jspui/handle/123456789/10676 | |
| dc.rights | Default Licence | - |
| dc.subject | hydroformylation | en |
| dc.subject | phosphine | en |
| dc.subject | chemistry | en |
| dc.subject | catalysts | en |
| dc.subject | density | en |
| dc.title | Exploring the forces that control the P-C bond length in phosphamides and their complexes: The key role of hyperconjugation | en |
| heal.abstract | The factors tuning the R(P-C) bond length of the labile P-C bond in phosphamides have been explored by means of density functional theory, employing natural bond orbital (NBO) analysis. The second-order perturbation stabilization energy Delta E(2) due to hyperconjugation accounts well for the unusually long R(P-C) bond lengths in a series of phosphamides and related species. Favorable n(O) -> sigma*(P-C) interactions primarily affect the R(P-C) bond length through electron delocalization. Deleting these interactions from our calculations results in significant shortening of the P-C bond, to a bond length close to that of the P-C(sp(2)) bonds. This holds also true if n(O) is "screened" by protonation, while n(P) does not affect the strength of the P-C bond. Moreover, the linear correlations of R(P-C) vs Delta E(2) and of R(P-C) vs Delta E-del substantiate the validity of the concept that hyperconjugative interactions tune the P-C bond length in phosphamides and provide a novel explanation of P-C bond lability. It was found that the combination of electron- withdrawing substituents on the carbonyl C atom with electron- releasing substituents on the P atom strengthen the P-C bond, thus stabilizing phosphamides. Phosphamides could also be stabilized by coordination with early-transition-metal ions (e.g. [CpTiCl2{kappa O-1-H2PC(O)Me}](+)) but are destabilized upon coordination with late-transition-metal ions (e.g. [Ag{kappa O-1-MeC(O)PH2}](+) and [Cu{kappa P-2,O-MeC(O)PH2}](+)). The coordination of phosphamides with Rh(III) in [CpRhCl2{kappa P-1-H2PC-(OH)CH3}](+) only marginally affects the R(P-C) bond length. Finally, the interaction of phosphamides with the hard Li+, K+, and Tl+ cations does not affect significantly the n(O) -> sigma*(P-C) hyperconjugative interactions, and therefore, the R(P-C) bond length is only slightly shortened. | en |
| heal.access | campus | - |
| heal.fullTextAvailability | TRUE | - |
| heal.identifier.primary | Doi 10.1021/Om0600137 | - |
| heal.identifier.secondary | <Go to ISI>://000237592800014 | - |
| heal.identifier.secondary | http://pubs.acs.org/doi/abs/10.1021/om0600137 | - |
| heal.journalName | Organometallics | en |
| heal.journalType | peer reviewed | - |
| heal.language | en | - |
| heal.publicationDate | 2006 | - |
| heal.recordProvider | Πανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείας | el |
| heal.type | journalArticle | - |
| heal.type.el | Άρθρο Περιοδικού | el |
| heal.type.en | Journal article | en |
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