Structural and spectroscopic trends in mononuclear arylchalcogenolato-palladium(II) and -platinum(II) complexes: Crystal structures of [M(TeAr)2(dppe)] {M = palladium, platinum; Ar = phenyl, 2-thienyl; dppe = 1,2-bis(diphenylphosphino)ethane}

A series of mononuclear [M(EAr)2(dppe)] [M = Pd, Pt; E = Se, Te; Ar = phenyl, 2-thienyl; dppe = 1,2-bis(diphenylphosphino)ethane] complexes has been prepared in good yields by the reactions of [MCl2(dppe)] and corresponding ArE− with a special emphasis on the aryltellurolato palladium and -platinum complexes for which the existing structural information is virtually non-existent. The complexes have crystallized in five isomorphic groups: (1) [Pd(SePh)2(dppe)] and [Pt(SePh)2(dppe)], (2) [Pd(TePh)2(dppe)] and [Pt(TePh)2(dppe)], (3) [Pd(SeTh)2(dppe)], (4) [Pt(SeTh)2(dppe)] and [Pd(TeTh)2(dppe)], and (5) [Pt(TePh)2(dppe)]. In addition, solvated [Pd(TePh)2(dppe)] · CH3OH and [Pd(TeTh)2(dppe)] · 1/2CH2Cl2 could be isolated and structurally characterized. The metal atom in each complex exhibits an approximate square-planar coordination. The Pd–Se, Pt–Se, Pd–Te, and Pt–Te bonds span a range of 2.4350(7)–2.4828(7) Å, 2.442(1)–2.511(1) Å, 2.5871(7)–2.6704(8) Å, and 2.6053(6)–2.6594(9) Å, respectively, and the respective Pd–P and Pt–P bond distances are 2.265(2)–2.295(2) Å and 2.247(2)–2.270(2) Å. The orientation of the arylchalcogenolato ligands with respect to the M(E2)(P2) plane has been found to depend on the E–M–E bond angle. The NMR spectroscopic information indicates the formation of only cis-[M(EAr)2(dppe)] complexes in solution. The trends in the 31P, 77Se, 125Te, and 195Pt chemical shifts expectedly depend on the nature of metal, chalcogen, and aryl group. Each trend can be considered independently of other factors. The 77Se or 125Te resonances appear as second-order multiplets in case of palladium and platinum complexes, respectively. Spectral simulation has yielded all relevant coupling constants.

Preparation, X-ray structures, and NMR spectroscopic properties of [M(EAr)2(dppe)] {E = Se, Te; Ar = Ph, 2-thienyl; dppe = 1,2-bis(diphenylphosphino)ethane} were systematically examined with a special emphasis on tellurolato complexes for which solid-state structural data are virtually non-existent.Figure optionsDownload as PowerPoint slide