SYNTHESIS AND DOUBLE C-H ACTIVATION OF PALLADIUM(II) COMPLEXES WITH THE CATIONIC LIGAND [TO3PCH2(PY-2)]-4, PY=PYRIDINE) - SOME EVIDENCE OF THE FORMATION OF A PALLADIUM(IV) COMPLEX - CRYSTAL AND MOLECULAR-STRUCTURES OF [PDCL2(PY(CH2PTO3)-2)2](CLO4)2-CENTER-DOT-4CL2CH2, )-C6H3(PTO2CH(PY-2')-2)ME-4)]2-CENTER-DOT-2CL2CH2, AND 2)-C6H3(PTO2CHCL(PY-2')-2)ME-4)]CENTER-DOT-CL2CH2( (TO=C6H4ME)

[PdCl2(NCPh)2] reacts with [To3PCH2(Py-2)]ClO4 (1:2) (To = C6H4Me-4, P y = pyridine) or with [To3PCH2(Py-2)]Cl (1:1) to give, respectively, t rans-[PdCl2{PY{CH2PTo3}-2}2](ClO4)2 (1) or [PdCl3{Py{CH2PTo3}-2}] (2). By reacting 1 with 1,8-bis(dimethylamino)naphthalene (1:2 or 1:4) or [To3PCH2(Py-2)]Cl with [PdCl2(NCPh)2] and Na2CO3 (1:1:1), the complex dCl{mu2-kappa3-C6H3{PTo2CH(Py-2')-2}Me-4{]2.1/2H2O (3) is obtained. Th is complex reacts (i) with PEt3 (1:2) to give 4-3)[PdCl{kappa2.C6H3{PT o2CH(Py-2')-2)Me-4}(PEt3)] (4), (ii) with AgClO4 and PEt3 (1:2:2) to g ive d{kappa3-C6H3{PTo2CH(Py-2')-2}Me-4}(PEt3)]2(ClO4)2 (5), (iii) with an excess Of Cl2 to give [PdCl2:kappa2-C6H3{PTo2CHCl(Py-2')-2}Me-4}] (6), and (iv) with NaI (1:2) to give [PdI{mu2-kappa3-C6H3{PTo2CH(Py-2' )-2{Me-4}12 (7). Complex 6 reacts with excess of NaI to give cis- [PdI 2{kappa2-C6H3{PTo2CHCl(Py-2')-2)Me-4}] (8). The crystal structures of 1.4Cl2CH2, 3.2Cl2CH2, and 8.Cl2CH2 were determined. [1: space group P1 BAR, a = 12.227(4) angstrom, b = 12.565(4) angstrom, c = 12.720(4) ang strom, a = 61.95(2)degrees, beta = 87.44(3)degrees gamma = 71.89(3)deg rees, V = 1627.2(9) angstrom3, Z = 1, R(int) = 0.024, R(F, >4sigma(F)) = 0.036. 3: space group C2/c, a = 23.597(6) angstrom, b = 8.385(2) an gstrom, c = 27.320(6) angstrom, beta = 99.93(2)degrees, V = 5325(2) an gstrom3, Z = 4, R(int) = 0.029, R(F, >4sigma(F)) = 0.028. 7: space gro up P1BAR, a = 10.379(3) angstrom, b = 11.961(4) angstrom, c = 14.289(4 ) angstrom, a = 105.03(3)degrees, beta = 97.87(3)degrees, gamma = 113. 87(3)degrees, V = 1506.8(8) angstrom3, Z = 2, R(int) = 0.026, R(F, >4s igma(F)) = 0.027.] Complex 1 adopts a trans geometry with short Pd-Cl and Pd-N bond distances [2.2886(11) and 2.035(3) angstrom, respectivel y]. The strong trans influence of the Pd-C(methine) and Pd-aryl bonds in complex 3 promotes the lengthening of both the Pd-Cl [2.3725(10) an gstrom] and the Pd-N [2.135(3) angstrom] bonds. In complex 8 the coord ination around the palladium atom is not exactly planar; the N atom li es 0.38 angstrom out of the plane of the other four atoms.