Synthesis, structural characterization, and density functional study of homo- and heteropolyhalide complexes of Cu-II with dien and dpta ligands: Crystal structure of [bis(3-aminopropyl)amine](bromo)(diiodobromo)copper(II)
Φόρτωση...
Ημερομηνία
Συγγραφείς
Chaviara, A. T.
Tsipis, A. C.
Cox, P. J.
Bolos, C. A.
Τίτλος Εφημερίδας
Περιοδικό ISSN
Τίτλος τόμου
Εκδότης
Περίληψη
Τύπος
Είδος δημοσίευσης σε συνέδριο
Είδος περιοδικού
peer reviewed
Είδος εκπαιδευτικού υλικού
Όνομα συνεδρίου
Όνομα περιοδικού
European Journal of Inorganic Chemistry
Όνομα βιβλίου
Σειρά βιβλίου
Έκδοση βιβλίου
Συμπληρωματικός/δευτερεύων τίτλος
Περιγραφή
Polyhalide mononuclear [CuX(L)(XY2)] and dinuclear [{CuX(L)}(2)(mu-XY2X)] C-II complexes [L = diethylenetriamine (dien) or dipropylenetriamine (dpta); X = Cl, Br and Y = Br, I} have been obtained by treating the precursor [CuX2(L)] complexes with Br-2 or I-2 in 1:1 and 2:1 molar ratios. The new homo- and heteropolyhalide Cu-II complexes, either mononuclear or dinuclear, were predicted to be five-coordinate Cu-II complexes exhibiting a distorted square-pyramidal configuration. DFT calculations at the B3LYP level of theory provided a satisfactory description of the structures of all complexes, while the distorted square-pyramidal structure of a representative complex, namely [CuBr(dpta)(BrI2)], was further substantiated by a single-crystal X-ray diffraction study. In the square-pyramidal structure of [CuBr(dpta)(BrI2), the basal plane of the pyramid involves three Cu-N contacts [1.990(7), 2.065(7), and 1.989(7) angstrom] from dpta and the Br(1) atom, while Br(2), which participates in the formation of the terminal [BrI2](-) ligand, occupies the apical position. The Cu-Br(1) and Cu-Br(2) bond lengths were found to be 2.5797(14) angstrom (terminal) and 2.735(14) angstrom (bridging), respectively, while the Br1-Cu-Br2 bond angle is 98.83(5)degrees. The terminal [BrI2](-) ligand is almost linear [Br-I-I bond angle of 174.48(3)degrees]. DFT calculations, spectroscopic measurements, including far-IR and EPR studies, and magnetic measurements of the dinuclear complexes predict that the bridging tetrabalide XY2X moiety adopts a linear configuration as well. The bonding, electronic, and related properties of the complexes are also discussed in the framework of density functional theory. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005).
Περιγραφή
Λέξεις-κλειδιά
copper, density functional calculations, halides, n ligands, quaternary ammonium polyhalides, copper(ii) complexes, benzyltrimethylammonium tribromide, magnetic-properties, response theory, polyiodides, spectra, diethylenetriamine, thermochemistry, reactivity
Θεματική κατηγορία
Παραπομπή
Σύνδεσμος
<Go to ISI>://000231995500013
http://onlinelibrary.wiley.com/store/10.1002/ejic.200500146/asset/3491_ftp.pdf?v=1&t=h0f8yjel&s=c172c47145fee2448f2546a4d1975ac25bdb82b1
http://onlinelibrary.wiley.com/store/10.1002/ejic.200500146/asset/3491_ftp.pdf?v=1&t=h0f8yjel&s=c172c47145fee2448f2546a4d1975ac25bdb82b1
Γλώσσα
en
Εκδίδον τμήμα/τομέας
Όνομα επιβλέποντος
Εξεταστική επιτροπή
Γενική Περιγραφή / Σχόλια
Ίδρυμα και Σχολή/Τμήμα του υποβάλλοντος
Πανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείας