Εξειδίκευση τύπου :	Άρθρο σε επιστημονικό περιοδικό
Τίτλος:	Tetrathiomolybdate Complexes of Rhodium(I) with Molybdenum-Rhodium Interactions
Δημιουργός/Συγγραφέας:	Xamonaki N. Asimakopoulos A. Balafas A. Dasenaki M. Choinopoulos I. Coco S. [EL] Σημαντήρας, Eμμανουήλ[EN] Simandiras, Emmanuel D. Koinis S.
Εκδότης:	American Chemical Society
Ημερομηνία:	2016
Γλώσσα:	Αγγλικά
ISSN:	0020-1669
DOI:	10.1021/acs.inorgchem.6b00072
Περίληψη:	The synthesis and characterization of the tetrathiomolybdatorhodium(I) monoanionic complexes [L2Rh(-S)2MoS2]- (L = CO (3), P(OPh)3 (4), P(O-o-Tol)3 (P(o-CH3C6H4)3; 5), P(OMe)3 (6), P(OEt)3 (7), P(O-i-Pr)3 (8); L2 = COD (1,5-cyclooctadiene; 2), cis-dppen (cis-Ph2PCH - CHPPh2; 9), dppe (Ph2PCH2CH2PPh2; 10), dppb (Ph2P(CH2)4PPh2; 11)) is presented. The complex 2 (NEt4+ salt) was characterized by X-ray diffraction analysis. A detailed DFT study of the electronic structures of 2-4 and 6-8 has revealed the existence of extended electron delocalization over the four-membered Rh(-S)2Mo ring and hence the possibility of electronic communication between the metal centers. The electronic spectra were studied with TDDFT calculations, and the main absorption band in the visible region was assigned to ν(Rh→Mo) electron transfer transition, which is actually a HOMO-LUMO transition. The ν(Rh→Mo) transition was found to correlate linearly both with Tolmans electronic parameter of the phosphite ligands and the calculated HOMO-LUMO gap of the complexes, rendering it a well-defined ligand electronic parameter, which describes the net donating ability of monodentate and bidentate ligands (CO, COD, phosphites, diphosphines). The study of the variation 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:	Inorganic Chemistry
Τόμος/Κεφάλαιο:	55
Τεύχος:	10
Σελίδες:	4771-4781
Θεματική Κατηγορία:	[EL] Φυσική και θεωρητική χημεία[EN] Physical and theoretical chemistry
Αξιολόγηση από ομότιμους (peer reviewed):	Ναι
Κάτοχος πνευματικών δικαιωμάτων:	© 2016 American Chemical Society.
Όροι και προϋποθέσεις δικαιωμάτων:	All Open Access, Green
Εμφανίζεται στις συλλογές:	Ινστιτούτο Θεωρητικής και Φυσικής Χημείας (ΙΘΦΧ) - Επιστημονικό έργο