A NEW EXAMPLE OF A PALLADIUM-ASSISTED ARYL REARRANGEMENT - SYNTHESIS AND REACTIVITY OF (2,3,4-TRIMETHOXY-6-X-PHENYL)PALLADIUM [X=CHO, CH=N(N-C10H21), CH=NC6H4(NH2)-2,C(0)ME] AND (3,4,5-TRIMETHOXY-2-X-PHENYL)PALLADIUM [X=CHO,CH=NC6H4(NH2)-2]COMPLEXES - CRYSTAL AND MOLECULAR-STRUCTURE OF [PD(KAPPA(3)-C6H(CH=NC6H4(NH2)2)-6-(OME)3-2,3,4)(PPH3)]CF3SO3, [PD(KAPPA(3)-C6H(CH=NC6H4(NH2)-2)-2-(OME)3-3,4,5)(PPH3)]CF3SO3, AND [PD(KAPPA(2)-C6H(C(0)ME)-6-(OME)3-2,3,4)(2,9-DIMETHYL-1,10-PHENANTHROLINE)]CF3SO3

The reaction of [Pd(R)Cl(bpy)] [R = C6H(CHO)-6-(OMe)3-2,3,4; bpy = 2,2'-bipyridine] (1) with AgClO4 results in the O-coordination of the formyl group and the isomerization of the aryl ring to give [Pd(kappa2-R')(bpy)]ClO4 (2) [R'= C6H(CHO)-2-(OMe)3-3,4,5]. [HgR2] or [Hg(R)Cl] reacts with n-decylamine or o-phenylenediamine to give respectively [Hg(RN)2] (3) [RN = C6H{CH=N(n-C10H21)}-6-(OMe)3-2,3,4] or [Hg(RNN)Cl] (4) [RNN = C6H{CH=N(C6H4(NH2)-2}6-(OMe)3-2,3,4]. [PdCl2(MeCN)2] reacts with 3 to give [Pd(kappa2-RN)(mu-Cl)]2 (5) and with 4, PPh3, and K(CF3SO3) giving [Pd(kappa3-RNN)(PPh3)]CF3SO3 (6). The reaction of 5 with AgClO4 and, after removal of AgCl, with 2,2'-bipyridine (bpy) gives [Pd(kappa2-RN)(bpy)]ClO4 (7). [Pd(kappa2-R')(mu-Cl)]2 (8) reacts with o-phenylenediamine to give [Pd(kappa3-R'NN)Cl] (9) [R'NN = C6H{CH=NC6H4(NH2)-2}-2-(OMe)3-3,4,5] which reacts with PPh3 in the presence of K(CF3SO3), yielding [Pd(kappa3-R'NN)(PPh3)]CF3SO3 (6'). [Hg(RMe)Cl] (10) [RMe = C6H{C(O)Me}-6-(OMe)3-2,2,3,4] can be obtained by direct mercuriation of 3,4,5-trimethoxyacetophenone with Hg(MeCO2)2 and subsequent treatment with KCl. [Hg(RMe)2] (11), obtained by symmetrization of 10 with Me4NCl, reacts with [PdCl2(MeCN)2] or aqueous [PdCl4]2- to give the cyclometalated [Pd-(kappa2-RMe)(mu-Cl)]2 (12) which reacts with bpy or 2,9-dimethyl-1,10-phenanthroline (dmphen), giving the neutral complexes [Pd(RMe)Cl(N-N)] [N-N = bpy (13), dmphen (14)]. 13 and 14 react with Ag(CF3SO3), giving the cationic cyclometalated compounds [Pd(kappa2-RMe)(N-N)]CF3SO3 [N-N = bpy (15), dmphen (16)]. The structures of 6.CH2Cl2, 6'.Et2O, and 16.CH2Cl2 have been determined by X-ray crystallography at -95-degrees-C. Crystal data for 6.CH2Cl2: space group P1BAR, a = 12.452(3) angstrom, b = 12.754(3) angstrom, c = 13.275(3) angstrom, alpha = 111.34(2)degrees, beta = 104.21(2)degrees, gamma = 95.32(2)degrees, V = 1846.5 angstrom3, Z = 2, R(int) = 0.033; R(F, >4sigma(F)) = 0.040. Crystal data for 6'.1.5Et2O: space group P2(1)/c, a = 11.228(6) angstrom, b = 16.818(6) angstrom, c = 22.650(9) angstrom, beta = 101.61(4)degrees, V = 4190 angstrom3, Z = 4, R(int) = 0.033, R(F, >4sigma(F)) = 0.050. Crystal data for 16.CH2Cl2: space group P2(1)/n, a = 12.199(4) angstrom, b = 7.801(3) angstrom, c = 30.9 10(11) angstrom, beta = 95.80(3)degrees, V = 2927 angstrom3, Z = 4, R(int) = 0.061, R(F, >4sigma(F) = 0.050. The three complexes show distorted square planar geometries.