200009-40-1Relevant academic research and scientific papers
A new access to palladium-phosphine chemistry. Formation of polynuclear palladium compounds via the oxidation of ligands in simple palladium(ii) complexes
Su, Weiping,Cao, Kong,Hong, Maochun,Wu Daxu,Lu, Jiaxi
, p. 1527 - 1532 (2000)
The reactions of [Pd(dppp)(edt)] 1 or [Pd(dppp)(pdt)] 2 (edt2- = ethane-1, 2-dithiolate, pdt2- = propane- 1, 3-dithiolate, dppp = l, 3-bis(diphenylphosphino)propane) with oxygen or elemental Se under different reaction conditions gave rise to a series of polynuclear palladium complexes. The oxidation of 1 by oxygen in alkaline DMF solution yielded a dinuclear complex with sulfinato ligand, [Pd2(O2SCH2CH2SO 2)(edt)(dppp)] 3, while that of 2 afforded a hexanuclear complex, [Pd6(pdt)6]4. The molecular structure of 3 consists of two fragments [Pd(O2SCH2CH2SO2)] and [Pd(dppp)]2+, which are linked by an edt2- bridging ligand. The structure of 4 is made up of [Pd(pdt)] nits forming a cyclic neutral complex, of which the Pd6S12 core possesses pseudo D6d symmetry and six Pd atoms form a nearly regular six-membered ring with Pd ... Pd distances ranging from 3.050 to 3.090 A. The treatment of 2 with elemental Se in the ratios 1:1 and 1:1 generated [Pd2(dppp)2(pdt)]Cl2 5 and [Pd3(dppp)2(pdt)2]Cl2 6, respectively. The molecular structure of 5 and 6 can be considered as two fragments [Pd(dppp)]2+ linked by pdt2- and [Pd(pdt)2]2-, respectively. The reaction of 1 with 0.5 equivalent Se led to formation of [Pd2(dppp)2(edt)]Cl2 7. The molecular structure of 7 is quite similar to that of 5. All palladium atoms in the complexes are four-co-ordinated with distorted square-planar geometry. The complexes 1, 3-7 have been characterized by NMR, IR and electronic spectra. The Royal Society of Chemistry 2000.
