Syntheses, crystal and solution structures, ligand-exchange, and ligand coupling reactions of mixed pentaarylantimony compounds

Abstract

All possible combinations of mixed pentaarylantimony compounds bearing p-methylphenyl and p-trifluoromethylphenyl groups were synthesized: Ar nTol5nSb (n = 0-5: Ar=pCF3C 6H4, Tol=p-CH3C6H4): Tol5Sb (1), ArTol4Sb (2), Ar2Tol3Sb (3), Ar3Tol2Sb (4), Ar4TolSb (5). and Ar 5Sb (6). Compounds 2-5 are the first well-characterized examples of mixed acyclic pentaarylantimony species. The structures of 2-6 were determined by X-ray crystallography to feature trigonal-bipyramidal (TBP) geometry with the more electronegative p-trifluoromethylphenyl substituents selectively occupying the apical positions. Consideration of the chemical shifts of the ipso carbons of the aryl and tolyl groups suggested that the solution structures of 1-6 were also TBP. although their pseudorotation could not he frozen even at -80 °C. Ligand-exchange reactions (LERs) took place between 1 and 6 at ≈60°C in [D6]benzene und all six species 1-6 were found in the equilibrium mixture. The relative stabilities of 1-6 were determined quantitatively by comparison of the observed molar ratios of 1-6 in equilibrium with calculated statistical molar ratios, and Ar2Tol3Sb (3) was found to be the most stable. The ligand-coupling reactions (LCRs) of 2-5 in solution were greatly accelerated by adding Cu(acac)2 or Li + TFPB- (TFPB: [3,5-(CF3)2C6H3] 4B), whereby the rate becomes comparable to the LER. The use of flash vacuum thermolysis (FVT) allowed the LCR to occur with very little ligand-exchange: the exception ArTol4Sb had very fust ligand-exchange. The selectivities of the LCRs were calculated from the yield of the biaryls synthesized by using FVT. These results were highly consistent with reactions catalyzed in solution, in which bitolyl was not obtained at all. The experimental results suggested that the LCR of pentaarylantimony compounds proceeds in the manner of apical-apical coupling. © 2007 Wiley-VCH Verlag GmbH & Co. KGaA.