190021-72-8Relevant academic research and scientific papers
Photochemical Synthesis of cis,trans,cis-1,2,3,4-Tetrakis(diphenylphosphanyl)buta-1,3-diene and Its Metal Coordination
Prock, Johannes,Ehrmann, Katharina,Viertl, Wolfgang,Pehn, Richard,Pann, Johann,Roithmeyer, Helena,Bendig, Marvin,Rodríguez Villalón, Alba,Kopacka, Holger,Dumfort, Alexander,Oberhauser, Werner,Clausing, Simon T.,Kn?r, Günther,Brüggeller, Peter
, p. 4962 - 4971 (2018/11/23)
The new bis(bidentate) tetraphosphane cis,trans,cis-1,2,3,4-tetrakis(diphenylphosphanyl)buta-1,3-diene (dppbd) (7) was obtained by applying a photochemical synthetic protocol. The key step of the photochemical reaction consisted of an intramolecular [2+2] cycloaddition involving a C–C double and triple bond of the Pt-dimer species of the formula [Pt2Cl4(dppa)(trans-dppen)] (2) {dppa = 1,2-bis(diphenylphosphanyl)acetylene and dppen = 1,2-bis(diphenylphosphanyl)ethene} leading to [Pt2Cl4(dppbd)] (5). The asymmetrically bridged precursor complex 2 was obtained by combinatorial chemistry. Single crystal X-ray structure analyses of 2 and 5 proved that the intramolecular photochemical reaction occurred. Cyanolysis of 5 gave 7, which was oxidized to dppbdO4 (8). Compounds 7, 8, and the PdII dimer complex [Pd2Cl4(dppbd)] (9) were characterized in the solid state by a single-crystal X-ray structure analysis. Interesting photophysial properties emerged from the UV/Vis spectra acquired for 7 and the dimer Os complexes meso-Δ,Λ/Λ,Δ-[Os2(bpy)4(dppbd)](PF6)4 (10) and rac-Δ,Δ/Λ,Λ-[Os2(bpy)4(dppbd)](PF6)4 (11).
Synthesis of heterobimetallic bis(diphenylphosphino)acetylene-bridged palladium-platinum complexes. Crystal and molecular structure of [PdPtCl4(Ph2PC≡CPPh2) 2]·2CHCl3
Clark, Howard C.,Ferguson, George,Kapoor, Pramesh N.,Parvez, Masood
, p. 3924 - 3928 (2008/10/08)
Reaction of [(PMe2Ph)PdCl(μ-Cl)2PtCl(PMe2Ph)] (I) with 1,2-bis(diphenylphosphino)acetylene yields the heterobimetallic complex [Cl2Pd(Ph2PC≡CPPh2)2PtCl 2] (II). Solution studies using 31P and 195Pt NMR spectra reveal that II exists in an equilibrium of the type 2[Cl2Pd(Ph2PC≡CPPh2)2PtCl 2] ? [Cl2Pd(Ph2PC≡CPPh2)2PdCl 2] + [Cl2Pt(Ph2PC≡CPPh2)2PtCl 2]. Crystals of II [as the bis(chloroform) solvate] are monoclinic, space group P21/n with two formula units in a cell of dimensions a = 14.415 (3) A?, b = 12.149 (3) A?, c = 15.949 (3) A?, and β= 91.33 (2)°. The bimetallic complex lies about a crystallographic inversion center, and the Pd and Pt atoms are mutually disordered. The structure was solved by the heavy-atom method and refined by full-matrix least-squares calculations with anisotropic thermal parameters; R = 0.033 and Rw = (ΣwΔ2/ΣwF02)1/2 = 0.044 for 2407 observed reflections. The unique metal atom has slightly distorted square-planar geometry with mean M-Cl = 2.344 (2) A and mean M-P = 2.244 (2) A?. The strained 10-membered PtPdP4C4 ring system is nonplanar; there is significant bowing of the P-C≡C-P moiety [mean P-C ≡C = 172.2 (3)°] and enlargement of the M-P-C(acetylene) angles from tetrahedral [mean value 121.3 (2)°].
