Observation and theoretical analysis of the “sensitive coordination sites” in the isopolyoxomolybdate cluster [Mo₃₆O₁₁₂(H₂O)14]^8-

Long, D.-L. , Streb, C., Kögerler, P. and Cronin, L. (2006) Observation and theoretical analysis of the “sensitive coordination sites” in the isopolyoxomolybdate cluster [Mo₃₆O₁₁₂(H₂O)14]^8-. Journal of Cluster Science, 17(2), pp. 257-266. (doi: 10.1007/s10876-006-0058-9)

Abstract

Two isopolyoxomolybdate {Mo₃₆} cluster compounds are presented, where one incorporates two sodium ions into the {Mo₃₆} cluster cavity and the other does not, showing different “sensitive coordination sites ” to organic cation ligands TEAH⁺ (protonated triethanolamine) as identified by X-ray crystallography, and rationalized by DFT calculations. The compound (TEAH)₆{Na₂ [Mo₃₆O₁₁₂(H₂O)₁₄]}· 28H₂O (<b>1</b>) crystallizes in the trinclinic space group <i>P</i>−1, <i>a</i>=15.8931(2)Å, <i>b</i>=17.3089(2)Å, <i>c</i>=18.1880(3)Å, α = 101.210(1), β = 95.481(1), γ = 116.585(1)º <i>V</i>=4292.95(10)ų, <i>D</i>_c=2.688 g cm^-3. 16838 unique reflections and 1213 refined parameters were used in structure refinement. <i>R</i>1=0.032, <i>R</i>2=0.071. When sodium is eliminated from the reaction system, the new compound (TEAH)₈[Mo₃₆O₁₁₂ (H₂O)₁₄]· 10 H₂O (<b>2</b>) was also isolated and crystallographically characterized. Compound <b>2</b> crystallizes in the monoclinic space group <i>P</i>-1, <i>a</i>=16.3351(3)Å, <i>b</i>=16.5709(4) Å, <i>c</i>=18.5803(5)Å, <i>V</i>=4524.08(18)ų, <i>D</i> _c=2.525 g cm^{− 3}. 17591 unique reflections and 1016 refined parameters were used in structure refinement. <i>R</i>1=0.044, <i>R</i>2=0.128.

• Item Type: Articles
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Long, Dr Deliang and Cronin, Professor Lee and Streb, Mr Carsten
• Authors: Long, D.-L., Streb, C., Kögerler, P., and Cronin, L.
• Subjects: Q Science > QD Chemistry
• College/School: College of Science and Engineering > School of Chemistry; University Centres > Glasgow Materials Research Initiative
• Journal Name: Journal of Cluster Science
• Publisher: Kluwer Academic Publishers-Plenum Publishers
• ISSN: 1040-7278
• ISSN (Online): 1572-8862