Platinum(II) and Mixed Platinum(II)/Gold(I) σ-Alkynyl Complexes. The First Anionic σ-Alkynyl Metal Polymers

This is the authors' abstract. We don't add key points for this paper.

The alkynes C 6 Me 4 (C⋮CH) 2 -1,4, C 6 Me 4 (C⋮CH) 2 -1,2, and C 6 Me 3 (C⋮CH) 3 -1,3,5 react with cis -[PtCl 2 (PAr 3 ) 2 ] and NHEt 2 and a catalytic amount of CuI to give complexes trans -[Pt(C⋮CC 6 Me 4 C⋮CH-4) 2 (PAr 3 ) 2 ] [Ar = Ph ( 1a ), C 6 H 4 Me-4 (To) ( 1b )], trans -[Pt(C⋮CC 6 Me 4 C⋮CH-2) 2 (PAr 3 ) 2 ] [Ar = Ph ( 2a ), To ( 2b )], and trans -[Pt{C⋮CC 6 Me 3 (C⋮CH) 2 -3,5} 2 (PAr 3 ) 2 ] [Ar = Ph ( 3a ), To ( 3b )], respectively. The reactions of [Au(acac)PAr 3 ] (acac = acetylacetonato) with complex 1a or 1b (2:1) or with 3b (4:1) give the neutral mixed Pt II Au I 2 or Pt II Au I 4 σ-alkynyl complexes trans -[Pt(C⋮CC 6 Me 4 C⋮CAuPAr 3 -4) 2 (PAr 3 ) 2 ] [Ar = Ph ( 4a ), To ( 4b )] or trans -[Pt{C⋮CC 6 Me 3 (C⋮CAuPTo 3 ) 2 -3,5} 2 (PTo 3 ) 2 ] ( 5b ), respectively. Additionally, the replacement of the triarylphosphine ligands present in 1a, 2a, 4b, or 5b with various trialkylphosphines produces the homologous derivatives with PMe 3 ( 1c, 2c, 4c, 5c ), PEt 3 ( 1d ), or P( n Bu) 3 ( 1e), respectively. PPN[Au(acac) 2 ] reacts with complex 1a, 1c, or 1e (1:1) to give (PPN) n [ trans -Pt{(C⋮CC 6 Me 4 C⋮C-4) 2 Au}(PR 3 ) 2 ] n [R = Ph ( 6a ), Me ( 6c ), n Bu ( 6e )], while its reaction with 3b (2:1) produces (PPN) 2 n [ trans -Pt{C⋮CC 6 Me 3 (C⋮C) 2 -3,5Au 2 (PTo 3 ) 2 ] n ( 7 ). Complexes 6a, 6c, 6e, and 7 are the first anionic σ-alkynyl metal polymers described so far. The crystal structures of 1a ·CHCl 3, 2b ·2CHCl 3, and 4b ·5CH 2 Cl 2 have been determined. Each complex displays crystallographic inversion symmetry.