ChemInform Abstract: Synthesis, Solid-State and Solution Structure, and Physicochemical Properties of the Iodide-Bridged Face-Sharing Bioctahedral Molybdenum(III) Dimers (Cat)+(Mo2I7(PMe3)2)- (Cat: PHMe3, NMe4, AsPh4).

ChemInform Abstract

(Ia) (yield given in mg) is prepared from Mo₂I₄(PMe₃)₄ and I2 in toluene and crystallizes in the space group P2₁/n with Z=4. The reaction of MoI₃(THF)₃ with PMe₃ and (NMe₄)I in THF affords (Ib), while (Ic) (space group P21212, Z=2) is obtained from (Ib) by metathesis with (AsPh₄)Cl. The phosphine ligands are in the syn configuration in the solid state. Dissolution causes an equilibrium with the gauche isomer to the statistical 1:2 mixture. The compounds show a temp.-dependent paramagnetism. A variable-temp. ¹H NMR study is reported.