Mössbauer and X-ray photoelectron spectroscopies (XPS) are complemented with high-level quantum-chemical computations in the study of the geometric and electronic structure of the paramagnetic salt of the metallacarborane sandwich complex [Fe(1,2-C2B9H11)2]Cs = FeSanCs. Experimental 57Fe isomer shifts and quadrupole splitting parameters are compared with the theoretical prediction, with good agreement. The appearance of two sets of Cs(3d) doublets in the XPS spectrum, separated by 2 eV, indicates that Cs has two different chemical environments due to ease of the Cs(+) cation moving around the sandwich complex with low-energy barriers, as confirmed by quantum-chemical computations. Several minimum-energy geometries of the FeSanCs structure with the corresponding energies and Mössbauer parameters are discussed, in particular the atomic charges and spin population and the surroundings of the Fe atom in the complex. The Mössbauer spectra were taken at different temperatures showing the presence of a low-spin Fe atom with S = 1/2 and thus confirming a paramagnetic FeIII species.

Departamento de Física Facultad de Ciencias Exactas y Naturales Universidad de Buenos Aires Ciudad Universitaria 1428 Buenos Aires Argentina

Departamento de Química Física Facultad de Ciencia y Tecnología Universidad del País Vasco Apartado Postal 644 E 48080 Bilbao Spain

Institute of Inorganic Chemistry of the Czech Academy of Sciences CZ 250 68 Řež near Prague Czech Republic

Instituto de Física de Buenos Aires Consejo Nacional de Investigaciones Científicas y Técnicas Ciudad Universitaria 1428 Buenos Aires Argentina

Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas Universidad Nacional de La Plata CCT La Plata Consejo Nacional de Investigaciones Científicas y Técnicas Diag 113 y 64 Sucursal 4 CC 16 1900 La Plata Argentina

Instituto de Química Física Rocasolano CSIC E 28006 Madrid Spain

Instituto de Química Médica CSIC E 28006 Madrid Spain

Theoretical Chemistry and Computational Modelling Doctoral School Universidad Autónoma de Madrid 28049 Madrid Spain

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