Reactivity of ortho-substituted aryl-palladium complexes towards carbodiimides, isothiocyanates, nitriles, and cyanamides.

Complexes [Pd(C(6)H(3)XH-2-R'-5)Y(N;N)] (X=O, NH; Y=Br, I; R'=H, NO(2); N;N=N,N,N',N'-tetramethylethylenediamine (tmeda), 2,2'-bipyridine (bpy), 4,4'-di-tert-butyl-2,2'-bipyridine (dtbbpy)) react with RN=C=E (E=NR, S) or RC identical withN (R=alkyl, aryl, NR''(2)) and TlOTf (OTf=CF(3)SO(3)) to give, respectively, 1) products of the insertion of the C=E group into the C--Pd bond, protonation of the N atom, and coordination of X to Pd, [Pd{kappa(2)-X,E-(XC(6)H(3){EC(NHR)}-2-R'-4)}(N;N)]OTf or [Pd(kappa(2)-X,N-{ZC(6)H(3)(NH=CR)-2-R'-4})(N;N)]OTf, or products of the coordination of carbodiimides and OH addition, [Pd{kappa(2)-C,N-(C(6)H(4){OC(NR)}NHR-2)}(bpy)]OTf; or 2) products of the insertion of the C identical withN group to Pd and N-protonation, [Pd(kappa(2)-X,N-{XC(6)H(3)(NH=CR)-2-R'-4})(N;N)]OTf.

Foot schwannomas that mimic nerve-entrapment syndromes: a report of three cases.

Schwannomas of the foot are rare. We describe three cases that mimicked compressive neuropathy, two resembling tarsal tunnel syndrome and a third resembling Morton's neuroma. All three patients had complete resolution of their pain after resection of the tumor.

An unusual palladium complex involved in an unusual rearrangement of ortho-palladated aryldithioacetals.

The reaction of 1 with Pd(dba)(2), Tl(TfO) and PPh(3) in 1:1:1:2 molar ratios to give 3 implicates (i) an oxidative addition reaction, (ii) a rearrangement involving the cleavage of one HC-S bond and formation of an aryl-S bonds, and (iii) coordination of the Pd(PR(3))(2) group with a ligand intermediate between eta(2)-[ArCH=S((+))To] and kappa(2)-C,S-ArCH((-))STo, which requires the consideration of 3 as intermediate between a Pd(0) and a Pd(II) complex. The coordination of the ligand as a chelating three-membered ring, instead of the expected five-membered ring involving C(10) and S(1), and the partial intramolecular redox process are explained as a consequence of the transphobia of the pair of ligands Ph(3)P/CH(STo)Ar.