Catenation of transition metal chalcogenide clusters and its electron

2003 Fiscal Year Final Research Report Summary

• Project/Area Number: 14540523
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: OKAYAMA UNIVERSITY OF SCIENCE
• Principal Investigator: AKASHI Haruo OKAYAMA UNIVERSITY OF SCIENCE, Research Institute of Natural Sciences, Associate Professor, 自然科学研究所, 助教授 (30221708)
• Project Period (FY): 2002 – 2003
• Keywords: transition metal / chalcogenide cluster / electron function / catenation

Research Abstract

Twin-cubane-type complex[{Mo_3RhCp^*S_4(H_2O)_7(O)}_2]^<8+> (2)was isolated from a reaction of[Mo_3S_4(H_2O)_9]^<4+>(1) and [(Cp^*RhCl_2)_2] in an acidic aqueous solution. The p-toluenesulfonate of the complex,[{Mo_3RhCp^*S_4(H_2O)_7(O)}_2](CH_3C_6H_4SO_3)_8 14H_2O([2](pts)_8・14H_O0), crystallized in the triclinic space group P1-(#2) with a=12.2631(8) Å,b=15.911(1) Å,c=17.389(3) Å,α=63.704(3)°,β=78.688(2)°,γ=81.038(2)°,V=3026.3821Å^3. The Mo_3RhCp^*S_4 moieties are dimerized into oxo-bridged twin-cubane-type core in the reaction. Very strong acidity of the Cp^*Rh group and relatively high oxidation states of molybdenum atoms causes a deprotonation at the water molecules, which coordinated to the molybdenum atom. This deprotonation reaction afforded[Mo_3RhCp^*S_4(H_2O)_7(OH)_2]^<4+> as an intermediate. Dehydration condensation of the two molecules of the intermediate gave[2](pts)_8・14H_2O. The Mo-O_<(bridge)> distances in [2](pts)_8-14H_2O are 1.901(6) Å and 1.891 (6) Å. The Mo-O_<(bridge)>-Mo angle(164.3(3)°) is nearly linear. This result is clearly shows that the basicity of the oxygen atoms in the bridges is weak. No protonation at the oxygen atom was observed even in strong acidic solution. If chloride ions are present.(>0.5 M), One mole of the complex 2 gives two moles of[Mo_3RhCp^*S_4(H_2O)_7Cl_2]^<4+>(3).