The mono-and bis(aryl)platinum(II) complexes [PtX(C6H3{CH2NMe2)z-2,6)] (X = halide) and z-2,6)] (R = phenyl, 4-tolyl) react with Clz and Brz or CuClz to yield the mono-and bis(aryl)platinum(IV) products [PtX3(C6H3{CH2NMez)z-2,6)] (2) and [PtRXz(C6H3~CHzNMez)z-2,6)] (5), respectively. The structural features of two representative compounds of 2 and 5 were studied by X-ray crystal structure determinations of 2a (X = C1) and of 5d (R = 4-tolyl, X = I). Crystals of 2a are monoclinic, space group Pn, with a = 13.759 (16), b = 7.950 (2), c = 7.244 (2) A, / 3 = 103.20 (4)O, and 2 = 2. A total of 2050 reflections have been used in the refinement, resulting in a final R = 0.039. The platinum center has a distorted octahedral geometry having a mer coordination of the (C6H3(CHzNMe2)z-2,6) (abbreviated NCN) ligand via C(ipso) (1.96 (3) A) and the two mutually trans positioned NMez roups. There is a atoms (2.324 (4) and 2.329 ( 5 ) A). Crystals of 5d are hexagonal, space group R3, with a = 37.463 (7), c = 7.908 (3) A, and 2 = 18. A total of 755 reflections have been used in the refinement, resulting in a final R = 0.024. The structure of 5d shows a mer coordination of the NCN li and (Pt-C(ipso) 2.00 (2) A), one axial iodide (Pt-I 2.811 (3) A), and one meridial iodide (Pt-I 2.813 (3) 1). The remaining axial position is occupied by a 4-tolyl group (Pt-C(ipso) 2.12 (3) A). The cis orientation of the aryl groups (C(ips0)-Pt-C'(ips0) 94 (1)') is noteworthy and is the result of the fixed attachment of the NCN ligand to the Pt(1V) center. The NMe2 groupings of the latter ligand hinder rotation of the 4-tolyl group along the Pt-C(ipso) axis ('H NMR 6 H(2) 6.01 and 6 H(6) 8.94). On the basis of extensive product formation studies it is concluded that the oxidative addition reactions of dihalogens to square-planar platinum(I1) complexes proceed via the S N 2 type mechanism, usually leading to trans-X2 arrangements in the product. When steric factors prevent this configuration or when the trans-X2 product is thermodynamically unstable, cis-X2 products are found. In the case of formation of 5d, this reaction is a unique route for synthesizing the complex, as any attempt to prepare this compound by substitution of Br in [PtBr,(NCN)] by 4-tolyl in reactions with 4-tolyllithium failed. significant difference in Pt-Cl bond lengths between the meridial C1 atom (2.445 (7) 1 ) and the axial C1 CH Utrecht, T h e Netherlands. processes are stabilized by the NCN ligand and can be isolated. An example is the isolation of stable squarepyramidal Pt(I1)-Hg(I1) intermediates from reactions of [PtBr(NCN)] with mercury(I1) formamidino, triazenido, and carboxylato compounds, which provides evidence that dinuclear Pt-Hg compounds are key intermediates in reactions between neutral organoplatinum(I1) complexes and mercury salt^.^-^(1) (a) van Koten, G.; Timmer, K.; Noltes, J. G.; Spek, A. L. J. Chem. Soc., Chem. Commun. 1978,250. (b) Grove, D. M.; van Koten, G.; Ubbels, H. J. C.; Spek, A. L. (2) van der Ploeg, A. F. M. J.; van Koten, G.; Vrieze, K.; Spek, A...