Synthesis, Crystal Structure, and Relativistic DV-Xα Calculation of a μ-Oxido-μ-molybdato(VI)-bridged Dinuclear Oxidomolybdenum(V) Complex with 2-(3-Aminopropyl)aminoethanethiol

抄録

A μ-O-μ-Mo^VIO₄-bridged dinuclear oxidomolybdenum(V) complex with 2-(3-aminopropyl)aminoethanethiol (Hapaet), [Mo₃O₇(apaet)₂]·2CH₃OH, was prepared. The crystal structure was determined by the single-crystal X-ray diffraction method at 293 K. It crystallizes in the monoclinic space group P2₁/n with a = 16.558(3)Å, b = 8.9725(13)Å, c = 17.193(3)Å, β = 90.192(2)°, V = 2554.3(7)ų, D_x = 1.899 g/cm³, and Z = 4. The R1 [I > 2σ(I)] and wR2 (all data) values are 0.0331 and 0.0768, respectively, for all 6166 independent reflections. The two molybdenum atoms are bridged by an oxido-O atom and MoO₄²⁻ in a distorted octahedral geometry with oxido-O and meridional NNS-donor atoms of apaet⁻. A relativistic DV-Xα calculation supported the Mo^V₂Mo^VI mixed-valent state.