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Synthesis and Characterization of Hypervalent Organoantimony(III) Compounds Containing the [2‐(Me 2 NCH 2 )C 6 H 4 ] 2 Sb Fragment
Author(s) -
Opris Laura M.,
Preda Ana Maria,
Varga Richard A.,
Breunig Hans J.,
Silvestru Cristian
Publication year - 2009
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.200801129
Subject(s) - chemistry , hypervalent molecule , antimony , stibine , intramolecular force , aryl , crystal structure , crystallography , nitrogen , square pyramidal molecular geometry , stereochemistry , alkyl , moiety , x ray crystallography , medicinal chemistry , inorganic chemistry , organic chemistry , catalysis , diffraction , reagent , physics , arsine , phosphine , optics
Compounds containing the [2‐(Me 2 NCH 2 )C 6 H 4 ] 2 Sb moiety were prepared by using R 2 SbX [X = Cl ( 1 ), Br ( 2 )] as starting materials. The reaction of 1 with Me 3 SiCH 2 MgCl gave the mixed alkyl–aryl stibine R 2 SbCH 2 SiMe 3 ( 3 ). Reduction of 2 with Mg in thf followed by in situ air oxidation or treatment with S 8 resulted in the isolation of (R 2 Sb) 2 E [E = O ( 4 ), S ( 5 )]. Compound 5 is also formed from R 2 SbCl and Na 2 S. The reaction of 4 with [W(CO) 5 (thf)] gives the unexpected complex [(R 2 SbOH)W(CO) 5 ] ( 6 ). The new compounds were investigated by IR, 1 H, and 13 C NMR spectroscopy, as well as by mass spectrometry. The structures of 3 – 6 were determined by single‐crystal X‐ray diffraction. For compounds 3 – 5 , both nitrogen atoms from the pendant arms are involved in intramolecular N→Sb coordination, which results in distorted square‐pyramidal (C,N) 2 SbC or (C,N) 2 SbE (E = O, S) cores. By contrast, in 6 only one nitrogen atom is strongly coordinated to the antimony center, whereas the second nitrogen atom is involved in N ··· H–O bonding. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)