The synthesis of the isoindolinimines (5) by the insertion of isocyanides into the metal-carbon bond of the ortho-palladated primary benzylamine complex ( l a ) is described; the novel oxidative addition and subsequent reductive elimination of the ortho-metallated primary benzylamine-platinum complex (6) yields 3-0x0-I ,2,3,4-tetra hydroisoqu i no1 ine (8).
The reaction of t r a n ~-[ M ( h J H ~C H ~P h ) ~l ~] ( M = Pd or Pt) with two molar equivalents of AgBF4 leads to srtho-metallation of one of the phenyl rings of the benzylamine ligands. The X-ray structure ofshows the Pt to be in a planar molecule o-bonded to the phenyl ring. Crystals are orthorhombic, space group /barn, with a = 18.376( 8), b = 16.394( 5), c = 6.970(1) A, and Z = 8.037 for 1 071 observed [//a(/) 2 3.01 diffractometer data. Bond data include Pt-1 2.701 (1 ), Pt-C(carbony1) 1.842(16), Pt-C(aryl) 1.997(15), and Pt-N 2.053(13) A. The reaction of cis-[M(PMe2Ph),12] (M = Pd or Pt) with two molar equivalents of AgBF4 gives cations which catalyse the addition of water to dimethyl acetylenedicarboxylate. In the last century the reaction with silver ions of metal complexes containing halogen atoms was frequently used, and in 1938, King' reported that the reaction of [Pt-(NH3)2C12J with Ag+ in aqueous solution gave [Pt(NH,),-,I2 +. The reaction has been used with a range of amine complexes by Cleare who observed that the reaction is best carried out using iodide complexes rather than the chlorides, because of the lower solubility of silver iodide compared with silver chloride. We have found that in some solvents benzylamine complexes undergo ortho-metallation when the halide complexes are reacted with silver ion.
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