2024-03-28T23:42:04Zhttp://uvadoc.uva.es/oai/requestoai:uvadoc.uva.es:10324/334492021-06-24T07:42:57Zcom_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
https://doi.org/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