Zur Elektronenstruktur hochsymmetrischer Verbindungen der f‐Elemente. 38 [1] Kristall‐, Molekül‐ und Elektronenstruktur von Tris(hydrotris(1‐pyrazolyl)borato)‐samarium(III)
2005; Wiley; Volume: 631; Issue: 8 Linguagem: Inglês
10.1002/zaac.200500004
ISSN1521-3749
AutoresHauke Reddmann, Christos Apostolidis, Olaf Walter, J. Rébizant, H.‐D. Amberger,
Tópico(s)Organometallic Complex Synthesis and Catalysis
ResumoAbstract Electronic Structures of Highly Symmetrical Compounds of f Elements. 38 [1] Crystal, Molecular and Electronic Structure of Tris(hydrotris(1‐pyrazolyl)borato)samarium(III) Tris(hydrotris(1‐pyrazolyl)borato)samarium(III) (SmTp 3 ) crystallizes in the space group P6 3 /m (No. 176) with two molecules in the unit cell. The Sm 3+ central ion is coordinated by nine N atoms in the shape of a tricapped trigonal prism, leading to an effective crystal field (CF) of D 3h symmetry. The underlying CF splitting pattern was extracted from the absorption and luminescence spectra run at room and low temperatures, and simulated by fitting the free parameters of a phenomenological Hamiltonian achieving an r.m.s. deviation of 9.4 cm −1 for 58 assignments. The parameters used allow the estimation of the global ligand field strength experienced by the Sm 3+ central ion, the insertion of SmTp 3 into empirical nephelauxetic and relativistic nephelauxetic series, and the set‐up of experimentally based nonrelativistic and relativistic molecular orbital schemes in the f range.
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