J Am Chem Soc. 2001 Nov 07;123(44):10954-65. doi: 10.1021/ja003623l.

Synthesis, structure, and reactions of (acylimino)triaryl-lambda(5)-bismuthanes: first comparative study of the (acylimino)pnictorane series.

Journal of the American Chemical Society

Y Matano, H Nomura, H Suzuki, M Shiro, H Nakano

PMID: 11686699 DOI: 10.1021/ja003623l

Abstract

The synthesis, structure, and reactions of (acylimino)triaryl-lambda(5)-bismuthanes and a comparative study of the structure and reactivity of a series of (acylimino)pnictoranes are reported. Treatment of ortho-substituted triarylbismuth dichlorides 1 (Ar(3)BiCl(2); Ar = 2-MeC(6)H(4), 2-MeOC(6)H(4), 2,4,6-Me(3)C(6)H(2)) with amides 2 (H(2)NCOR; R = CF(3), CCl(3), 3,5-(CF(3))(2)C(6)H(3)) in the presence of 2.2 equiv of KO-t-Bu in dichloromethane afforded (acylimino)triaryl-lambda(5)-bismuthanes 3 (Ar(3)Bi=NCOR) in yields of 77-96%. The ortho-substituted aryl ligands and the electron-withdrawing N-substituents afford kinetic and thermodynamic stabilization, respectively, to the reactive Bi=N bond. The structures and properties of a series of (acylimino)pnictoranes (Ar(3)M=NCOR and H(3)M=NCOCF(3); M = P, As, Sb, Bi) are compared by IR and (13)C and (15)N NMR, X-ray crystallography, and ab initio molecular orbital calculations. It was found that the contribution of the M(+)-N=C-O(-) canonical form becomes more prominent and the single-bond character of the M=N bond increases progressively as the pnictogen atom becomes heavier. The Bi=N bond of (acylimino)-lambda(5)-bismuthanes 3 possesses a highly polarized single-bond character, probably due to the differences in orbital size and electronegativity between the bismuth and nitrogen atoms. Thermal decomposition of (aroylimino)triaryl-lambda(5)-bismuthane 3f (o-Tol(3)Bi=NCOAr; Ar = 3,5-(CF(3))(2)C(6)H(3)) produces a gel in dry conditions or aniline 12 (ArNH(2)) in slightly wet conditions with a good recovery of tris(2-methylphenyl)bismuthane (4a). It is likely that the aryl isocyanate 13 (ArNCO) is produced during the thermolysis via a concerted C --> N migration of the Ar group with an elimination of the triarylbismuthonio group as bismuthane 4a. (Acylimino)triaryl-lambda(5)-bismuthanes 3 oxidize 1,1,2,2-tetraphenylethanediol, benzenethiol, methanol, and ethanol to benzophenone, diphenyl disulfide, methyl formate, and acetaldehyde, respectively, in two different reaction pathways depending on the structure of the substrates. Compound 3d (o-Tol(3)Bi=NCOCCl(3)) transfers the nitrenoid moiety to triphenylphosphane, triphenylarsane, and tris(2-methylphenyl)stibane to give the corresponding (acylimino)pnictoranes (Ar(3)M=NCOCl(3); M = P, As, Sb) and 4a, suggesting that 3d is thermodynamically much less stable than their lighter pnictogen counterparts. The copper-catalyzed decomposition of 3 (o-Tol(3)Bi=NCOR) afforded N-acyl-o-toluidines 18 (o-TolNHCOR) via a Bi --> N migration of the tolyl group. The observed reactivities of (acylimino)triaryl-lambda(5)-bismuthanes 3 demonstrate a good leaving ability of the bismuthonio group.

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