All-Organometallic Analogues of Zeise's Salt for the Three Group 10 Metals (Journal article)

ForniΓ©s, J./ Martin, A./ Martin, L. F./ MenjΓ³n, B./ Tsipis, A. C.

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.
Institution and School/Department of submitter: Πανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείας
URI: https://olympias.lib.uoi.gr/jspui/handle/123456789/8921
Link: http://pubs.acs.org/doi/abs/10.1021/om0502077?journalCode=orgnd7
Publisher: American Chemical Society
Appears in Collections:Άρθρα σε επιστημονικά περιοδικά ( Ανοικτά)

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