[Mo3S4Cl3(dmpe)3]PF6 | 111618-77-0

• 英文名称: [Mo3S4Cl3(dmpe)3]PF6
• 英文别名: [Mo3S4Cl3(dmpe)3](PF6)
• CAS: 111618-77-0
• 化学式: C₁₈H₄₈Cl₃Mo₃P₆S₄*F₆P
• 分子量: 1117.83
• InChiKey: YRUJTBPOCYSCLI-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  sodium hydroxide 、 [Mo3S4Cl3(dmpe)3]PF6 以 水 、 乙腈 为溶剂， 反应 5.0h， 以93%的产率得到
  参考文献：
  名称：

  带有末端羟基和硫代基团的三核 Mo3S4 簇的合成、结构、气相反应性和催化相关性

  摘要：

  钼 (IV) 羟基 [Mo3S4(dmpe)3(OH)3]+ (1+) 和氢硫化物 [Mo3S4(dmpe)3(SH)3]+ (2+) [dmpe = 1,2-双（二甲基膦酰基）通过分别用氢氧化钠或氢硫化钠处理其氯化物前体，已经以高产率分离了乙烷]三金属立方体簇配合物。[1]BPh4 和 [2]PF6 的晶体结构证实 -QH (Q = O, S) 基团与金属中心配位。羟基和氢硫基 Mo3S4 簇复合物都可以通过光谱、质谱和 X 射线技术进行充分表征。介绍了使用 ESI 串联质谱法对 1+ 和 2+ 阳离子的气相解离进行的比较研究，并将结果与​​已报道的羟基钨类似物的结果进行比较。已经探索了 1+ 和 2+ 物种对乙醇和 1-戊硫醇的气相反应性。气相生成的 [Mo3S4(dmpe)2(O)(OH)]+ 阳离子通过与其钨同类物类似的机制激活乙醇分子。讨论了钼和钨簇硫化物在碰撞诱导解离 (CID)

  DOI：

  10.1002/ejic.201300890
• 作为产物：
  描述：

  六氟磷酸钾 、 molybdenum chloride sulphide 、 1,2-双(二甲基瞵)乙烷 以 乙腈 为溶剂， 以94%的产率得到[Mo3S4Cl3(dmpe)3]PF6
  参考文献：
  名称：

  High yield synthesis of trinuclear [M3S4X3(diphos)3]+ (M=Mo, W; X=Cl, Br and diphos=dmpe, dppe) molecular clusters from solid state materials. Synthesis and structure of [W3S4H3(dppe)3](BPh4)

  摘要：

  The excision of polymeric {M3S7X4}(x) (M = Mo. W; X = Cl, Br) cluster phases with diphosphines (dmpe, dppe) in acetonitrile affords a one step general synthetic route for the preparation of trinuclear molecular clusters with formula [M3S4X3(diphos)(3)](+) (M=Mo, W: X=Cl, Br and diphos = dmpe. dppe) in high yields, Following this strategy, the cluster cations [Mo3S4Br3(dmpe)(3)](+) and [W3S4Br3(dppe)(3)](+) have been prepared for the first time. This last tungsten cluster has proved to be a useful synthon for the synthesis of the hydride derivative [W3S4H3(dppe)(3)](+) in moderate yields. The crystal structure of [W3S4H3(dppe)(3)](BPh4) consists of a equilateral tungsten triangle with one capping and three bridging sulfur atoms defining a incomplete W3S4 cuboidal unit in which the tungsten and the sulfur atoms occupy adjacent vertex of a cube with a metal atom missing. The hydride ligand occupies the outer position of the metal in a pseudo-octahedral environment. The other two outer positions on each metal are occupied by the diphosphine phosphor us atoms. located one above and one bellow the M-3 plane resulting in two different P-31(H-1} NMR signals. Electrochemical studies for all trinuclear clusters reported show one quasi reversible and one irreversible reduction process. (C) 2001 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0277-5387(00)00640-9

文献信息

• Synthesis, Structure, and Optical-Limiting Properties of Heterobimetallic [M₃CuS₄] Cuboidal Clusters (M = Mo or W) with Terminal Phosphine Ligands
  作者：Marta Feliz、Juan M. Garriga、Rosa Llusar、Santiago Uriel、Mark G. Humphrey、Nigel T. Lucas、Marek Samoc、Barry Luther-Davies

  DOI：10.1021/ic010098y

  日期：2001.11.1

  Cubane-type clusters of formula [Mo(3)CuS(4)Cl(4)(dmpe)(3)](PF(6)) (4), [Mo(3)CuS(4)Br(4)(dmpe)(3)](PF(6)) (5), and [W(3)CuS(4)Br(4)(dmpe)(3)](PF(6)) (6) have been prepared by reacting the incomplete cuboidal trimers [Mo(3)S(4)Cl(3)(dmpe)(3)](PF(6)) (1), [Mo(3)S(4)Br(3)(dmpe)(3)](PF(6)) (2), and [W(3)S(4)Br(3)(dmpe)(3)](PF(6)) (3), respectively, with CuX (X = Cl or Br) or the mononuclear copper complex

  式[Mo（3）CuS（4）Cl（4）（dmpe）（3）]（PF（6））（4），[Mo（3）CuS（4）Br（4）（ dmpe）（3）] [PF（6））（5）和[W（3）CuS（4）Br（4）（dmpe）（3）]（PF（6））（6）的制备反应不完整的立方三聚体[Mo（3）S（4）Cl（3）（dmpe）（3）] [PF（6））（1），[Mo（3）S（4）Br（3）（dmpe ）（3）] [PF（6））（2）和[W（3）S（4）Br（3）（dmpe）（3）]（PF（6））（3），分别用CuX （X = Cl或Br）或在THF中的单核铜络合物[Cu（CH（3）CN）（4）]（+）。该反应的发生没有金属氧化态的整体变化，具有[M（3）CuS（4）]（5+）核的化合物4-6具有16 e（-）用于金属-金属键合。X射线结构分析4-6显示M（3）Cu单元的有效C（3v）对称性，MM距离在统计上对于M =
• Unsymmetrically Substituted Mo ₃ S ₄ ⁴⁺ Clusters Bearing Diphosphane Ligands
  作者：Ivan Sorribes、Rosa Llusar、Cristian Vicent

  DOI：10.1002/ejic.201201176

  日期：2013.3.12

  A unique series of unsymmetrically substituted [Mo3S4(dmpe)3Cl3–x(dca)x]PF6 (x = 0–3) clusters that feature mixed Cl/dca terminal ligands, prepared by thermal reaction of [Mo3S4(dmpe)3Cl3]PF6 ([1]PF6) [dmpe = 1,2-bis(dimethylphosphanyl)ethane] with sodium dicyanamide [Na(dca); dca = dicyanamide] is reported. The cluster/Na(dca) ratio, reaction time as well as the nature of the solvent dictate the relative

  一系列独特的不对称取代的 [Mo3S4(dmpe)3Cl3–x(dca)x]PF6 (x = 0–3) 簇具有混合的 Cl/dca 末端配体，由 [Mo3S4(dmpe)3Cl3]PF6 的热反应制备([1]PF6) [dmpe = 1,2-双（二甲基磷酰基）乙烷] 与双氰胺钠 [Na(dca); dca = 双氰胺] 报道。簇/Na(dca) 比率、反应时间以及溶剂的性质决定了 [Mo3S4(dmpe)3Cl2(dca)]PF6 ([2]PF6)、[Mo3S4(dmpe)3Cl(dca) )2]PF6 ([3]PF6) 和 [Mo3S4(dmpe)3(dca)3]PF6 ([4]PF6)。采用基于电喷雾电离质谱 (ESI-MS) 的方案对反应条件进行高通量优化，以最佳产率获得 [2–4] PF6。dca 的加入赋予 [2-4]PF6 系列显着的极性差异，因此，化合物 [2–4]PF6 可
• Heterometallic Cuboidal Clusters M₃M‘Q₄ (M = Mo, W; M‘= Sn, Pb, As, Sb; Q = S, Se):  From Coordination Compounds to Supramolecular Adducts
  作者：Rita Hernández-Molina、Irina V. Kalinina、Pavel A. Abramov、Maxim N. Sokolov、Alexandr V. Virovets、Javier G. Platas、Rosa Llusar、Victor Polo、Cristian Vicent、Vladimir P. Fedin

  DOI：10.1021/ic701581u

  日期：2008.1.1

  Reactions of the incomplete cuboidal clusters [M(3)Q(4)(acaC)(3)(PY)(3)](+) (M = Mo, W; Q = S, Se) with group 14 and 15 metal complexes with the S(2)p(0) electronic configuration (AsPh3, SbPh3, SbCl3, Sbl(3), Pbl(3)(-), SnCl3-) led to heterometal incorporation with the formation of cuboidal clusters of the type [M-3(EX3)Q(4)(acac)(3)(py)(3)](n+) (n = 0 for Sn, Pb; n = 1 for As, Sb), whose structures were determined by X-ray diffraction. The cuboidal clusters can be described as complexes of the cluster tridentate ligand [M(3)Q(4)(acac)(3)(PY)(3)](+) (mu(2)-chalcogen atoms as donors) with the EX3, where the E atom attains a distorted octahedral coordination. Analysis based on the bond distances E-Q gives the following sequence of affinity: As < Sb; Pb < Sn approximate to Sb; SbPh3 < Sbl(3) approximate to SbCl3; W3S4 < W3Se4. Interaction energies at the gas phase between [W(3)Q(4)(acac)(3)(py)(3)](+) (Q = S, Se) and SbX3 (X = 1, Ph) were computed at the DFT level (BP86/TZP). The magnitude of the interaction depends strongly on the substituents at Sb, and the replacement of iodine by the phenyl group decreases the interaction energy from -9.21 to -2.70 kcal/mol and from -12.73 to -3.85 kcal/mol for the W3SbS4 and W3SbSe4 cores, respectively.
• Heterobimetallic cuboidal [Mo3NiS4] and [W3NiS4] cluster diphosphane complexes as molecular models in hydrodesulfurization catalysis
  作者：Marta Feliz、Rosa Llusar、Santiago Uriel、Cristian Vicent、Michael Brorson、Konrad Herbst

  DOI：10.1016/j.poly.2005.04.004

  日期：2005.7

  Treatment of the cationic, incomplete cubane-type sulfido clusters [M3S4X3(diphos)(3)](+) (M = Mo, W; X = Cl, Br; diphos = dmpe (1,2-bis(dimethylphosphanyl)ethane), dppe (1,2-bis(diphenylphosphanyl)ethane)) with an excess of [Ni(cod)(2)] (cod = 1,5-cyclooctadiene) afforded the heterobimetallic single cube clusters [M3NiS4X3(diphos)(3)(CH3CN)](+) as PF6- salts. The acetonitrile ligand could be substituted by pyridine, tetrahydrothiophene and carbon monoxide in CH2Cl2 at room temperature, modelling the catalytic sites of heterogeneous Ni-MoS2 hydrodesulfurization catalysts. X-ray crystal structure analyses of [MO3NiS4Cl3(dmpe)(3)(CH3CN)]BPh4 and [W3NiS4Br3(dmpe)(3)(CO)]PF6 are reported. Electrochemical studies by cyclic voltammetry reported for all heterobimetallic [M3NiS4] clusters show two quasireversible oxidation processes, the molybdenum complexes being ca. 0.2 V more difficult to oxidize than the tungsten analogues. (c) 2005 Elsevier Ltd. All rights reserved.
• Mixed-Metal Assemblies Based on Cyanide-Bridged Cubane-Type Mo₃CuS₄/Mo₃S₄ Clusters and Molybdenum Carbonyls
  作者：Rosa Llusar、Ivan Sorribes、Cristian Vicent

  DOI：10.1021/ic9002302

  日期：2009.6.1

  The substitutional lability of Mo-Cl and Cu-Cl bonds in cubane-type Mo3CuS4 and incomplete cubane-type Mo3S4 clusters is exploited in an attempt to prepare cyanide-terminated complexes, namely [Mo3S4(CuCN) (dmpe)(3)Cl-3]PF6 ([2]PF6) and [Mo3S4(dmpe)(3)(CN)(3)]PF6 ([5]PF6), and to subsequently use them as precursors in low-dimensional linking reactions. Mixed-metal assemblies formulated as [Mo3S4(Cu-mu CN center dot center dot center dot Mo(CO)(5)) (dmpe)(3)Cl-3](+) ([3](+)) and [Mo3S4(dmpe)(3)(mu CN center dot center dot center dot Mo(CO)(5))(3)](+) ([6](+)) are obtained by reaction of tetrahydrofuran solutions of [2]BPh4 and [5]BPh4 with the complex (THF)Mo(CO)(5). The intrinsic stability of the (M'-mu CN center dot center dot center dot Mo (CO)(5)) linkages (M'= Cu in 3(+) and Mo in 6(+)) in solution and in the gas phase is investigated through a combination of variable-temperature P-31 NMR, IR, UV-vis spectroscopies, and electrospray ionization tandem mass spectrometry. The spectroscopic and electrochemical consequences of CN coordination as well as Mo(CO)(5) ligation either at the Cu or the Mo site in Mo3CuS4 and Mo3S4 clusters are reported. Replacement of Cl by CN or CN center dot center dot center dot Mo(CO)(5) at the Cu site does not affect the redox potentials, whereas analogous substitution at Mo sites exerts a profound anodic shift of 220 and 500 mV upon Cl to CN and Cl to CN center dot center dot center dot MO(CO)(5) replacement, respectively.