Syntheses,Structures And Properties Research Of Carbonyl Metal Derivatives Of Polyoxomolybdates

The reaction of Na₂MoO₄·2H₂O/?NH₄?₆Mo₇O₂₄·4H₂O with Na₂TeO₃/TeO₂/Sb₂O₃ andMn?CO?₅Br/Re?CO?₅Cl in a mixed solvent solution led to the isolation of three series of novel polyoxomolybdate-based carbonyl metal derivatives,which have been thoroughly characterized by IR,elemental analysis,electrochemistry,UV-vis spectroscopy,X-ray single-crystal analysis,and catalysis studies.1.Three monomeric novel tellurium-containing heteropolymolybdate-supported carbonyl metalderivatives,?NH₄?₅H₃[(Te₂Mo₁₂?OH?O₄₄)?Mn?CO?₃?]·18H₂O?1?,?NH₄?₈[(Te₂Mo₁₂?OH?O₄₄)?Re?CO?₃?]·13H₂O?2?and?TMA?₅[(TeMo₉O₃₂)?Re?CO?₃?]·4H₂O?3?have been successfully isolated in good yield.Compounds 1 and 2 are isostructural,composed by[Te₂Mo₁₂?OH?O₄₄]^9-anion supporting[M?CO?₃]⁺?M=Mn?1?,Re?2??unit.The irregular[Te₂Mo₁₂?OH?O₄₄]^9–(Te₂Mo₁₂)framework comprises one upper[TeMo₃?OH?O₁₂]^3–?TeMo₃?moiety and one lower[TeMo₇O₂₉]^12–?TeMo₇?part,which are aggregated together by two corner-sharing{MoO₆}octahedral.Alternatively,structural analysis reveals that the structure of{[TeMo₃?OH?O₁₂][Mn?CO?₃]}^2–resembles to our previously reported cluster{[PMo₃O₁₆][Re?CO?₃]₄}^5–but with subtle differences.Compound 3 is assembled by[Re?CO?₃]⁺supportted on like three vacanies Keggin-type[TeMo₉O₃₂]^6-unit.2.Three novel antimony-containing heteropolymolybdate-supported metal carbonyl derivatives:?TMA?₃H[(SbMo₉O₃₂)?Re?CO?₃?₂]·5H₂O?4?,?TMA?₃[?Na₂?H₂O?₄??Na?H₂O?₄?-[(SbMo₉O₃₂)?Mn?CO?₃?]·5H₂O?5?and?TMA?₄[(Sb₂Mo₈O₃₀)?Mn?CO?₃?₂]?6?have been obtained successfully for the first time.The structure of compound 4 anion{SbMo₉}is similar to 3,except that the anion of 4 is composed of{SbMo₉}carrying one[Re?CO?₃]⁺group on the upper and lower parts thereof.The anion structure of compound 5 is similar to 3,interestingly,the{[SbMo₉O₃₂][Mn?CO?₃]}^6-forms a1-D chainlike structure by bridging a three-nuclears Na cluster.The anion structure of compound 6 is similar to 4 and can be seen as{SbMo₉Re₂}substituted with one Sb atom.3.One Lindqvist-type monolacunary isopolymolybdate-based carbonyl manganese compoundhas been synthesized:?TMA?₂[(H₂Mo₅O₁₈)?Mn?CO?₃?₂]·H₂O?7?.X-ray single-crystal analysis indicates that the polyanion{[Mo₅O₁₈][Mn?CO?₃]₂}^4-?7a?consists of a[Mo₅O₁₈]^6-block supporting two[Mn?CO?₃]⁺groups.The two[Mn?CO?₃]⁺groups are bonded to[Mo₅O₁₈]^6-by three bridged oxygen bonds,respectively.Different from the well-known cluster the two[Mn?CO?₃]⁺groups in 7a are additionally connected together by a?₂-oxo atom,forming a dinuclear Mn2 segenment.