All-Organometallic Analogues of Zeise's Salt for the Three Group 10 Metals
Φόρτωση...
Ημερομηνία
Συγγραφείς
ForniΓ©s, J.
Martin, A.
Martin, L. F.
MenjΓ³n, B.
Tsipis, A. C.
Τίτλος Εφημερίδας
Περιοδικό ISSN
Τίτλος τόμου
Εκδότης
American Chemical Society
Περίληψη
Τύπος
Είδος δημοσίευσης σε συνέδριο
Είδος περιοδικού
peer reviewed
Είδος εκπαιδευτικού υλικού
Όνομα συνεδρίου
Όνομα περιοδικού
Organometallics
Όνομα βιβλίου
Σειρά βιβλίου
Έκδοση βιβλίου
Συμπληρωματικός/δευτερεύων τίτλος
Περιγραφή
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.
Περιγραφή
Λέξεις-κλειδιά
Θεματική κατηγορία
Παραπομπή
Σύνδεσμος
http://pubs.acs.org/doi/abs/10.1021/om0502077?journalCode=orgnd7
Γλώσσα
en
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Όνομα επιβλέποντος
Εξεταστική επιτροπή
Γενική Περιγραφή / Σχόλια
Ίδρυμα και Σχολή/Τμήμα του υποβάλλοντος
Πανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείας