185225-47-2Relevant articles and documents
Preparation of buta-1,3-diynyl complexes of platinum(II) and their use in the construction of neutral molecular squares: Synthesis, structural and theoretical characterisation of cyclo-{Pt(μ-C≡CC≡C)(dppe)}4 and related chemistry
Bruce, Michael I.,Costuas, Karine,Halet, Jean-Francois,Hall, Ben C.,Low, Paul J.,Nicholson, Brian K.,Skeltone, Brian W.,White, Allan H.
, p. 383 - 398 (2007/10/03)
Copper(I)-catalysed reactions of cis-PtCl2(L)2 (L= PEt3, L2 = dppe, dppp) with buta-1,3-diyne have given the corresponding diynyl complexes, cis-Pt(C≡CC≡CH)2(L)2 (L= PEt3 1, L2 = dppe 2, dppp 3) whose solid-state structures have been determined from single crystal X-ray diffraction studies. Theoretical calculations were carried out to probe the electronic structure of these diynyl complexes. Complex 2 reacts with Co2(CO)8 to give a bis-adduct 5 and with Ru3(μ-dppm)(CO)10 to give a mono-adduct 6; in both, the least hindered C≡C triple bond(s) is(are) coordinated. Lithiation (LiBut) of 2 gives a dilithio derivative, which has been converted to dimethyl 7 or mono-SiMe3 8 or -Au(PPh3) 9 complexes. Cu(I) and Ag(I) (MI) adducts (quot;tweezerquot; complexes) have been obtained from reactions of 2 with MISCN or [MI(NCMe)4]+. An ES mass spectrometric study of the interactions of 2 with Group 1 cations and with Tl+ is also described; comparative experiments with {W(CO)3Cp}2(μ-C8), in which the four C≡C triple bonds do not have a "tweezer" conformation, have also been carried out. The degree of association is determined by the competitive solvation of the Group 1 cation. Coupling of the buta-1,3-diynyl complexes with Pt(OTf)2(L′)2 gives homo- or mixed-ligand molecular squares cyclo-{(L)2Pt(μ-C≡CC≡C)2Pt(L′) 2}2 (L, L′ = PEt3, L2, L′2 = dppe, dppp; not all combinations), of which the molecular structure of cyclo-{Pt(μ-C≡CC≡C)(dppe)}4 17 is described (as solvates containing dmso). The molecular squares form adducts with substituted ammonium triflates [NH2R2][OTf] (R = Et, Pri, Cy; NH2R2 = dbuH) and with Group 11 cations [MI(NCMe)]+.
