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Spontaneous vs. Base‐Induced Dehydrochlorination of Group 14 ortho ‐Carboranylamidinates
Author(s) -
Harmgarth Nicole,
Liebing Phil,
Förster Andreas,
Hilfert Liane,
Busse Sabine,
Edelmann Frank T.
Publication year - 2017
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.201700500
Subject(s) - chemistry , disproportionation , deprotonation , triethylamine , crystallography , ligand (biochemistry) , trigonal bipyramidal molecular geometry , nuclear magnetic resonance spectroscopy , stereochemistry , base (topology) , medicinal chemistry , crystal structure , catalysis , organic chemistry , ion , mathematical analysis , biochemistry , receptor , mathematics
The reaction of the lithium ortho ‐carboranylamidinate Li[HL] {HL = [ o ‐C 2 B 10 H 10 C(N i Pr)(NH i Pr)]} with ECl 2 R 2 (E = Si, Ge, Sn, Pb; R = Cl, Me, Bu, Ph) leads to new ortho ‐carboranylamidinates of the group 14 elements. In the case of the heavier elements, Ge, Sn, and Pb, compounds of the composition R 2 ECl[HL] were obtained in a straightforward manner, where the E atom adopts trigonal‐bipyramidal coordination. In the case of Si, disproportionation to R 2 Si[L] and H 2 L takes place immediately. The R 2 Si[L]‐type compounds, in which the Si atom exhibits a tetrahedral coordination, were obtained in a targeted synthesis protocol by reaction of the doubly lithiated ligand Li 2 L with R 2 SiCl 2 . The heavier homologues Cl 2 Ge[L] and Cl 2 Sn[L](THF) have been obtained accordingly. In contrast, it was found that deprotonation of R 2 ECl[HL] to R 2 E[L], employing triethylamine as a base, is not appropriate. All new compounds have been characterized by single‐crystal X‐ray diffraction, IR spectroscopy, and NMR spectroscopy, as well as mass spectrometry.