Structure and Properties of Lantern‐Shaped Hexapalladium Complexes with Germylene and Thiolate Ligands [Pd6(µ‐GePh2)2(µ‐SC6H4‐p‐X)2(CN‐C6H3Me2‐2,6)8] (X = NO2, Cl, H, CH3)

Abstract

Reaction of diaryl disulfides, ArSSAr (Ar = C6H4‐p‐Cl, Ph, C6H4‐p‐CH3) with a hexapalladium complex with bridging germylene ligands, [Pd6(µ‐GePh2)2(CN‐C6H3Me2‐2,6)8(µ‐CN‐C6H3Me2‐2,6)2] (1) afforded arylthiolate‐bridged complexes, [Pd6(µ‐GePh2)2(µ‐SAr)2(CN‐C6H3Me2‐2,6)8] (Ar = C6H4‐p‐Cl, Ph, C6H4‐p‐CH3) (3–5). The Pd(0)4Pd(I)2 complexes as well as analogous complex with 4‐nitrophenylthiolate ligands [Pd6(µ‐GePh2)2(µ‐SC6H4‐p‐NO2)2(CN‐C6H3Me2‐2,6)8] (2) have a hexagonal bipyramidal structure which contains two bridging thiolate ligands at basal coordination sites. Electrochemical measurement of 2–5 showed one reversible redox wave at E1/2 = –0.51 (2), –0.61 (3), –0.66 (4) and –0.70 (5) V (vs. Fc+/Fc) in the oxidation region, and irreversible reduction peak at Epc = –2.04 (2), –2.29 (3), and –2.38 (4) V (vs. Fc+/Fc) in the reduction region. Both oxidation and reduction potentials are correlated well with Hammett substitution constant σp of the aryl group of the thiolate ligands.