2026-04-30T05:15:49Zhttps://uvadoc.uva.es/oai/request

oai:uvadoc.uva.es:10324/334492025-03-26T19:10:04Zcom_10324_1186com_10324_931com_10324_894com_10324_28542com_10324_952col_10324_1404col_10324_28543

Xamonaki, Nikoletta Asimakopoulos, Anastasios Balafas, Anastasios Dasenaki, Marilena Choinopoulos, Ioannis Coco Cea, Silverio Simandiras, Emmanuel Koinis, Spyros 2018-12-13T12:11:41Z 2018-12-13T12:11:41Z 2016 Inorganic Chemistry, 2016, 55 (10), pp 4771–4781 0020-1669 http://uvadoc.uva.es/handle/10324/33449 10.1021/acs.inorgchem.6b00072 Producción Científica The synthesis and characterization of the tetrathiomolybdatorhodium(I) monoanionic complexes [L2Rh(μ-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(μ-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 Tolman’s 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. application/pdf eng American Chemical Society info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by-nc-nd/4.0/ Attribution-NonCommercial-NoDerivatives 4.0 International Interacciones Molibdeno-Rodio Molybdenum–Rhodium Interactions Tetrathiomolybdate Complexes of Rhodium(I) with Molybdenum–Rhodium Interactions info:eu-repo/semantics/article https://pubs.acs.org/doi/10.1021/acs.inorgchem.6b00072 SI