All-Organometallic Analogues of Zeise's Salt for the Three Group 10 Metals
| dc.contributor.author | ForniΓ©s, J. | en |
| dc.contributor.author | Martin, A. | en |
| dc.contributor.author | Martin, L. F. | en |
| dc.contributor.author | MenjΓ³n, B. | en |
| dc.contributor.author | Tsipis, A. C. | en |
| dc.date.accessioned | 2015-11-24T16:45:22Z | |
| dc.date.available | 2015-11-24T16:45:22Z | |
| dc.identifier.uri | https://olympias.lib.uoi.gr/jspui/handle/123456789/8921 | |
| dc.rights | Default Licence | - |
| dc.title | All-Organometallic Analogues of Zeise's Salt for the Three Group 10 Metals | en |
| heal.abstract | Ethene has been found to be able to split the electron-deficient pentafluorophenyl bridging system in [NBu4]2[{M(C6F5)2}(ΞΌ-C6F5)2] to give the corresponding mononuclear compounds [NBu4][M(C6F5)3(Ξ·2-C2H4)] (M = Pt (1), Pd (2)) in reasonable yield. Compounds 1 and 2 are well-behaved species and have been isolated and characterized by analytical and spectroscopic methods. The crystal structure of 2, as established by X-ray diffraction methods, reveals that the Pd atom is in an approximately SP-4 environment defined by the ipso-C atoms of the three Οƒ-bound C6F5 groups (C6F5-ΞΊ1) and the midpoint between the doubly bonded C atoms of the metal Ο€-bound ethene molecule (Ξ·2-C2H4). The ethene molecule is coordinated upright, and the CC bond length (133.6(6) pm) is the same as in the free ligand (133.7(2) pm). The nickel homologue [NBu4][Ni(C6F5)3(Ξ·2-C2H4)] (3), formed by the low-temperature reaction of [NBu4]2[Ni(C6F5)4] with B(C6F5)3 in the presence of C2H4, could not be isolated but only spectroscopically detected in solution. The experimentally established stability of the [M(C6F5)3(Ξ·2-C2H4)]- species has been found to follow the trend calculated by DFT methods for the M-(Ξ·2-C2H4) bond strength:"‰ Pt > Pd > Ni. Furthermore, quantitative estimates of back-bonding in the [M(C6F5)3(Ξ·2-C2H4)]- and [MCl3(Ξ·2-C2H4)]- anions were obtained using NBO analyses of electron populations of the relevant donorβ�’acceptor orbitals and the second-order stabilization energy associated with the charge transfer (CT) interactions describing the back-bonding phenomenon. | en |
| heal.access | campus | - |
| heal.fullTextAvailability | TRUE | - |
| heal.identifier.primary | 10.1021/om0502077 | - |
| heal.identifier.secondary | http://pubs.acs.org/doi/abs/10.1021/om0502077?journalCode=orgnd7 | - |
| heal.journalName | Organometallics | en |
| heal.journalType | peer reviewed | - |
| heal.language | en | - |
| heal.publicationDate | 2005 | - |
| heal.publisher | American Chemical Society | en |
| 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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