Synthesis and Study of Hexanuclear Molybdenum Clusters Containing Thiolate Ligands

Four hexanuclear molybdenum chloride cluster complexes containing terminal thiolate ligands have been synthesized and fully characterized. (Bu4N)2[Mo6Cl8(SEt)6] was prepared by reacting Na2[Mo6Cl8(OMe)6] with an excess of ethanethiol in refluxing tetrahydrofuran. (PPN)2[Mo6Cl8(SBu)6], (Bu4N)2[Mo6Cl8(SBn)6], and (Bu4N)2[Mo6Cl8(SNC8H6)6] (C8H6NS− = 3-indolylthiolate) were subsequently prepared in the reaction of [Mo6Cl8(SEt)6]2− with an excess of HSR (R = Bu, Bn or 3-indolyl). Single crystal X-ray diffraction analyses were performed on two of these complexes: (PPN)2[Mo6Cl8(SEt)6]·Et2O, crystallizes in the triclinic space group P1̅ with a = 12.3894(11), b = 13.7651(12), c = 15.0974(13), α = 103.975(2), β = 99.690(2), γ = 98.062(2), and Z = 1; (PPh3Me)2[Mo6Cl8(SBn)6]·2NO2CH3, also crystallizes in the P1̅ space group with a = 12.1574(16), b = 13.4441(17), c = 14.2132(18), α = 89.654(2), β = 88.365(2), γ = 71.179(2), and Z = 1. Our studies demonstrate that [Mo6Cl8(SEt)6]2− displays luminescent properties and that the same complex undergoes substitution reactions with different thiols, as well as reaction with electrophilic reagents such as MeI.

本研究成功合成并完成了四种含端基硫醇盐配体的六核氯化钼簇配合物的全面表征。(Bu₄N)₂[Mo₆Cl₈(SEt)₆]通过将Na₂[Mo₆Cl₈(OMe)₆]与过量乙硫醇在回流四氢呋喃中反应制得。后续通过[Mo₆Cl₈(SEt)₆]²⁻与过量HSR（R = Bu、Bn或3-吲哚基）反应，分别制备得到(PPN)₂[Mo₆Cl₈(SBu)₆]、(Bu₄N)₂[Mo₆Cl₈(SBn)₆]及(Bu₄N)₂[Mo₆Cl₈(SNC₈H₆)₆]（其中C₈H₆NS⁻为3-吲哚硫醇盐）。本研究对其中两种配合物开展了单晶X射线衍射分析：(PPN)₂[Mo₆Cl₈(SEt)₆]·Et₂O结晶于三斜晶系空间群P1̅，晶胞参数为a = 12.3894(11)、b = 13.7651(12)、c = 15.0974(13)，α = 103.975(2)°、β = 99.690(2)°、γ = 98.062(2)°，Z = 1；(PPh₃Me)₂[Mo₆Cl₈(SBn)₆]·2NO₂CH₃同样结晶于P1̅空间群，晶胞参数为a = 12.1574(16)、b = 13.4441(17)、c = 14.2132(18)，α = 89.654(2)°、β = 88.365(2)°、γ = 71.179(2)°，Z = 1。研究表明，[Mo₆Cl₈(SEt)₆]²⁻具有发光性能，该配合物可与不同硫醇发生取代反应，亦可与碘甲烷(MeI)等亲电试剂发生反应。