Some transition-metal complexes derived from the ligand [Ph3CS(CH2)2NHCH2]2CH2 and the crystal structure of [Pd{S(CH2)2NH(CH2)3NH(CH2)2SNi}2]2+

Abstract

S-Dealkylation of the ligand [Ph₃CS(CH₂)₂NHCH₂]₂CH₂ occurs when it is treated with certain bivalent metal ions (Ni²⁺, Cd²⁺, or Pd²⁺). The products are trimeric species of general form [M{[graphic omitted]}₂]²⁺(M = metal). By allowing the nickel trimer to react with Pd²⁺ or Cd²⁺, mixed-metal trimers were obtained of formula [M{[graphic omitted]i}₂]²⁺(M = Pd or Cd). The crystal structure of one such salt with M = Pd is reported. The associated anion consists of 38.5% Br^– and 61.5% NCS^–. The crystals are monoclinic, space group P2₁/c, with Z= 2, a= 7.957(8), b= 15.127(10), c= 10.988(11)Å, and β= 105.2(1)°. A total of 747 reflections above background have been refined to R 0.070. The cation has crystallographically imposed symmetry with the palladium atom in a planar S₄ environment [Pd–S 2.338(9), 2.337(9)Å]. The nickel atoms also have planar environments [Ni–S 2.182(11), 2.181(10); Ni–N 1.97(2), 1.96(2)Å] with the PdS₄ and NiS₂N₂ planes intersecting at an angle of 121°.