SYNTHESIS AND STUDY OF THE BENZYLPALLADIUM(IV) AND NAPHTHYLPALLADIUM(IV) COMPLEXES PDBRME2(CH2AR) (BPY2), PDBRME2(CH2AR) (PHEN2) AND MU-HYDROCARBYL PALLADIUM(IV)-PALLADIUM(IV) AND PALLADIUM(IV) PLATINUM(IV) COMPLEXES AND THE STRUCTURE OF FAC-PDBRME2(CH2-P-C6H4BR) (PHEN)

Benzyl and naphthyl bromides react with dimethylpalladium(II) complexes PdMe2(L2) (L2 = bpy, phen) to form the palladium(IV) complexes PdBrMe2(CH2Ar)(L2) (Ar = p-C6H4X (X = H, Me, Br, NO2), C6F5) and PdBrMe2(CH2Ar)(bpy) (Ar = 1-C10H7, 2-C10H7). The 2,2ʹ-bipyridyl complexes and PdBrMe2-(CH2C6F5)(phen) reductively eliminate ethane with formation of PdBr(CH2Ar)(bpy) and PdBr-(CH2C6F5)(phen), respectively, on warming to ca. 40 °C in (CD3)2CO. The other 1,10-phenanthroline complexes undergo less selective reductive elimination, to form PdBr(CH2Ar)(phen) and PdBrMe(phen) in a ca. 10:1 ratio (Ar = p-C6H4Me) and ca 3:1 ratio (Ar = p-C6H4X where X = H, Br, NO2). α,αʹ-Dibromo-m-xylene reacts with PdMe2(bpy) to form PdBrMe2(CH2-m-C6H4CH2Br)(bpy), and this complex undergoes further oxidative addition with MMe2(bpy) (M = Pd, Pt) to form the binuclear complexes (PdBrMe2(bpy))2(µ-m-(CH2)2C6H4) and (PdBrMe2(bpy))(PtBrMe2(bpy))(µ-m-(CH2)2C6H4). The complex PdBrMe2(CH2-p-C6H4Br)(phen) has a fac-PdC3 configuration with the Pd-Br bond (2.636 (1) Å) trans to the benzyl group. The Pd‒C(benzyl) bond (2.091 (6) Å) is ca. 0.06 Å longer than the Pd‒CH3 bonds. Crystals of PdBrMe2(CH2-p-C6H4Br)(phen) are monoclinic, space group P2l/n, with a = 8.465 (2) Å, b = 9.051 (2) Å, c = 26.364 (6) Å, β = 96.75 (2)°, and Z = 4. © 1990, American Chemical Society. All rights reserved.