Εξειδίκευση τύπου :	Άρθρο σε επιστημονικό περιοδικό
Τίτλος:	Heterotrimetallic tetrathiomolybdate and tetrathiotungstate complexes of rhodium(I) and copper(I) with Rh-Mo(W)-Cu interactions
Δημιουργός/Συγγραφέας:	Charalampous, Elena Xamonaki, Nikoletta Asimakopoulos, Anastasios Kritikou, Anastasia Bethanis, Kostas Chrissanthopoulos, Athanassios Choinopoulos, Ioannis [EL] Σημαντήρας, Eμμανουήλ[EN] Simandiras, Emmanuel D. Koinis, Spyros
Εκδότης:	Elsevier
Ημερομηνία:	2021
Γλώσσα:	Αγγλικά
ISSN:	02775387
DOI:	10.1016/j.poly.2021.115536
Περίληψη:	The synthesis and characterization of the monoanionic heterotrimetallic (d8···d0···d10) complexes [L2Rh(μ-S)2M(μ-S)2CuCl]− (L = P(OPh)3, P(O-o-Tol)3 (P(O-o-CH3C6H4)3), P(OMe)3, P(OEt)3, P(OiPr)3; L2 = COD (1,5-cyclooctadiene), cis-dppen (cis-Ph2PCH = CHPPh2); M = Mo, W) is presented. The complex (NEt4)[(cis-dppen)Rh(μ-S)2W(μ-S)2CuCl] was characterized by X-ray diffraction analysis. The detailed DFT study of the electronic structure of the complexes with P(OMe)3 and COD ligands has revealed the existence of extended electron delocalization over the atom-sharing (spiro) four-membered rings system Rh(μ-S)2M(μ-S)2Cu and the possibility of electronic communication between the terminal metal centers. The electronic spectra of the complexes with P(OMe)3 ligands were studied with TDDFT calculations and the main absorption band in the visible region was assigned to ν(Rh → Mo/W) electron transfer transition. The ν(Rh → Mo/W) transition was found to correlate linearly with Tolman’s electronic parameter of the phosphite ligands, making it an electronic parameter for the ligands studied. Finally, the study of the dependence of Δδ(31P) and 1J(Rh-P) of the phosphite complexes, with respect to the QALE model electronic parameters χd, πp and Ear, has succeeded in the assessment of the σ and π effects on these NMR spectral parameters.
Τίτλος πηγής δημοσίευσης:	Polyhedron
Τόμος/Κεφάλαιο:	210
Θεματική Κατηγορία:	[EL] Φυσική και θεωρητική χημεία[EN] Physical and theoretical chemistry [EL] Φασματοσκοπία[EN] Spectroscopy [EL] Χημεία (Γενικά)[EN] Chemistry (General)
Λέξεις-Κλειδιά:	Rhodium Copper Tetrathiomolybdate Tetrathiotungstate DFT Electronic communication Ligand electronic parameter P NMR QALE
Κάτοχος πνευματικών δικαιωμάτων:	© 2021 Elsevier Ltd
Ηλεκτρονική διεύθυνση στον εκδότη (link):	https://www.sciencedirect.com/science/article/pii/S0277538721005180
Εμφανίζεται στις συλλογές:	Ινστιτούτο Θεωρητικής και Φυσικής Χημείας (ΙΘΦΧ) - Επιστημονικό έργο