RESUMEN
The dialkyl malonate derived 1,3-diphosphines R2 C(CH2 PPh2 )2 (R=a, Me; b, Et; c, n-Bu; d, n-Dec; e, Bn; f, p-tolCH2 ) are combined with (p-tol3 P)2 PtCl2 or trans-(p-tol3 P)2 Pt((C≡C)2 H)2 to give the chelates cis-(R2 C(CH2 PPh2 )2 )PtCl2 (2 a-f, 94-69 %) or cis-(R2 C(CH2 PPh2 )2 )Pt((C≡C)2 H)2 (3 a-f, 97-54 %). Complexes 3 a-d are also available from 2 a-d and excess 1,3-butadiyne in the presence of CuI (cat.) and excess HNEt2 (87-65 %). Under similar conditions, 2 and 3 react to give the title compounds [(R2 C(CH2 PPh2 )2 )[Pt(C≡C)2 ]4 (4 a-f; 89-14 % (64 % avg)), from which ammonium salts such as the co-product [H2 NEt2 ]+ Cl- are challenging to remove. Crystal structures of 4 a,b show skew rhombus as opposed to square Pt4 geometries. The NMR and IR properties of 4 a-f are similar to those of mono- or diplatinum model compounds. However, cyclic voltammetry gives only irreversible oxidations. As compared to mono-platinum or Pt(C≡C)2 Pt species, the UV-visible spectra show much more intense and red-shifted bands. Time dependent DFT calculations define the transitions and principal orbitals involved. Electrostatic potential surface maps reveal strongly negative Pt4 C16 cores that likely facilitate ammonium cation binding. Analogous electronic properties of Pt3 C12 and Pt5 C20 homologs and selected equilibria are explored computationally.