New confacial bioctahedral diplatinum(IV) complexes with 3-aminoalkanethiolate bridges

Abstract

Reaction of [(PtlMe₃)₄] with the cyclic 3-aminoalkanethiol HSCH(CH₂CH₂)₂NMe, with the acyclic 3-aminoalkanethiol HS(CH₂)₃NMe₂, or with the sodium salt of each of these thiols, under various stoichiometries in organic solvents gave the complexes Na[(PtMe₃)₂{µ-SCH(CH₂CH₂)₂NMe}₃], [(PtMe₃)₂{µ-SCH(CH₂CH₂)₂NHMe}₃]l₂ and [(PtMe₃)₂{µ-S(CH₂)₃NHMe₂}₃]X₂(X = l or BPh₄). The complexes have been characterized by spectroscopic methods and the structures of two established by single-crystal X-ray diffraction. They consist of face-shared bioctahedral diplatinum(IV) complexes, in which the 3-aminothiolates function as bridging ligands through their sulfur atoms, to give a distorted-octahedral co-ordination of Pt with a fac-PtC₃S₃ configuration. In Na[(PtMe₃)₂{µ-SCH(CH₂CH₂)₂NMe}₃]·MeCN the nitrogen atoms of the ligands co-ordinate to the sodium cations to give a highly flattened trigonal-pyramidal geometry. In [(PtMe₃)₂{µ-S(CH₂)₃NHMe₂}₃][BPh₄]₂·MeCN the nitrogen atoms are protonated and take no part in co-ordination.