Publication detail

From Stiba- and Bismaheteroboroxines to N,C,N-Chelated Diorganoantimony(III) and Bismuth(III) Cations-An Unexpected Case of Aryl Group Migration

Year: 2015

Type of publication: článek v odborném periodiku

Name of source: Inorganic Chemistry

Publisher name: American Chemical Society

Place: Washington

Page from-to: 6010-6019

Titles:

Language	Name	Abstract	Keywords
cze	Ze Stiba- a Bismaheteroboroxínů k N,C,N-chelatovaným diorganoantimonitým a bismutitým kationtům	Byla studována možnost přípravy N,C,N-chelatovaných diorganoantimonitých a bismutitých kationtů ze Stiba- a Bismaheteroboroxínů.	Stibamaheteroboroxín; Bismaheteroboroxín; N,C,N-chelatovaný diorganoantimonitý; Bi; kationt
eng	From Stiba- and Bismaheteroboroxines to N,C,N-Chelated Diorganoantimony(III) and Bismuth(III) Cations-An Unexpected Case of Aryl Group Migration	An unprecedented transfer of an aryl group from boron to Sb and Bi is observed in the reaction of heteroboroxines of general formula ArM[(OBR)(2)O] [where M = Sb, Bi; Ar = C6H3-2,6-(CH2NMe2)(2); R = Ph, 4-CF3C6H4, 4-BrC6H4] with corresponding boronic acid RB(OH)(2). Using this procedure, ion pairs [ArMR](+)[R4B5O6](-) were obtained [where M = Sb and R = Ph (4), 4-CF3C6H4 (5), 4-BrC6H4 (6); where M = Bi and R = Ph (7), 4-CF3C6H4 (8), 4-BrC6H4 (9)]. All compounds were characterized using elemental analysis, electrospray ionization mass spectrometry, and multinuclear NMR spectroscopy, and molecular structures of 4 and 7 were determined by single-crystal X-ray diffraction analysis. The central metal atoms in 4-9 were arylated by respective boronic acids, which represents, to the best of our knowledge, unprecedented reaction path in the chemistry of heavier group 15 elements. Investigation of the mechanism of this transformation indicated that Lewis pairs consisting of monomeric oxides ArMO and boroxine rings are probably key intermediates. In this regard, molecular structures of ArSbO[(4-CF3C6H4)(3)B3O3].(4-CF3C6H4)B(OH)(2) (10) and {ArSbO[(3,5-(CF3)(2)C6H3)(3)B3O3]} (13) were established by single-crystal X-ray diffraction analysis, and compound 13 was also fully characterized in solution by multinuclear NMR spectroscopy. The bonding in 13 was analyzed in detail by using density functional theory and natural bond order calculations and compared with known adduct ArSbOB(C6F5)(3) (14) and hypothetical ArSbO monomer.	covalent organic frameworks; ncn-chelated organoantimony(iii); hydrogen storage materials; transition-state method; amine adducts; molecular-structure; structural-characterization; arylboronic acids; boronic acids; bond

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