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Steric Influence and Intermolecular Interactions of Formamidinate Ligands in Lanthanide (Sm, Yb) Arylchalcogenolate Complexes
Author(s) -
Ma YingZhao,
Pushkarevsky Nikolay A.,
Sukhikh Taisiya S.,
Galashov Arseniy E.,
Makarov Arkady G.,
Roesky Peter W.,
Konchenko Sergey N.
Publication year - 2018
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201800201
Subject(s) - chemistry , steric effects , lanthanide , intermolecular force , crystallography , moiety , coordination sphere , stereochemistry , molecule , atom (system on chip) , crystal structure , ion , organic chemistry , computer science , embedded system
The complexes [Ln(DippForm) 2 (QAr)(THF)] [DippForm = N , N′ ‐(2,6‐diisopropylphenyl)formamidinate; Ln = Sm, Yb; QAr = SPh, SePh, TePh, SeC 6 F 5 , Se( p ‐C 6 F 4 OMe)] were synthesized by reduction of corresponding dichalcogenides Ar 2 Q 2 with the Ln II formamidinates, [Ln(DippForm) 2 (THF) 2 ]. All complexes with QPh ligands have similar molecular structure (determined by X‐ray diffraction), they are mononuclear due to the effective shielding of the central atom by the bulky amidinate ligands, and possess transoid disposition of the latter. The complexes with fluorinated phenyl groups (Ar F ) possess an additional coordination of an o ‐F atom to the lanthanide ion. Only the compounds [Yb(DippForm) 2 (QAr F )(THF)] easily lose the coordinated THF due to the sterically crowded coordination sphere, and the addition of THF is reversible even at ambient temperature. The Sm compounds are stable towards elimination of THF upon moderate heating. Similar crystal packing is found for most of the complexes, except for [Sm(DippForm) 2 (SPh)(THF)], [Yb(DippForm) 2 (SeC 6 F 4 OMe)(THF)] and [Yb(DippForm) 2 (SeC 6 F 5 )], which was rationalized as a consequence of interaction of FormDipp ligands from neighboring molecules to form intermolecular junctions. Analogous junctions were found in the majority of known complexes with Ln(DippForm) 2 moiety (for all lanthanides). In the IR spectra the bands characteristic to the C–N, C–F and C–O bonds were revealed, some of which are noticeably influenced by the type of co‐ligands.