dimesityldioxomolybdenum(VI) | 60324-03-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: dimesityldioxomolybdenum(VI)
• 英文别名: dioxomolybdenum(VI)(2,4,6-Me3C6H2)2；dioxomolybdenum(VI)(mes)2；MoO2(2,4,6-Me3C6H2)2；MoO2(mes)2
• CAS: 60324-03-0
• 化学式: C₁₈H₂₂MoO₂
• 分子量: 366.311
• InChiKey: RGUGDPXCOREJQL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.33
• 重原子数：
  21.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  34.14
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  dimesityldioxomolybdenum(VI) 、 叔丁基异氰酸酯 以 not given 为溶剂， 生成 N-(tert-butyl)-2,4,6-trimethylbenzamide
  参考文献：
  名称：

  Unusual reactivity of isocyanates with dioxo- and diimidomolybdenum(VI) complexes

  摘要：

  Phenyl isocyanate reacts with dioxo- and diimidomolybdenum(VI) complexes such as Mo(O)2(mes)2 (1) (mes = mesityl = 2,4,6-C6H2Me3), Mo(mes)2CH2PBu3(O)2 (2), Mo(mes){CPBu3(mes)}(O)2(3) and Mo(NBu(t))2(mes)2 (4), selectively affording phenyl mesityl amide. This reaction proceeds via insertion into the Mo-mesityl bond, leading to an unstable oxazamolydenacycle which has been identified by C-13 NMR. This intermediate is probably hydrolysed with generation of the amide during chromatographic work-up.

  DOI：

  10.1016/s0277-5387(00)80213-2
• 作为产物：
  描述：

  、 Molybdenum, dichlorodioxobis(tetrahydrofuran)- 以 四氢呋喃 为溶剂， 以17%的产率得到
  参考文献：
  名称：

  摘要：

  The synthesis of known MoO(2)Mes(2) from MoO2Cl2 and MgMes(2) (1:1) in THF is accompanied by the formation of monomesityl molybdenum compounds. From ligand exchange and reduction arise [MesMoOCl(3)](-) (3a) and [MesMoO(3)](-) (3c). 3a and 3b crystallize in form of [(MesMoO(3))(2)[Mg2Cl2(THF)(5)](2)][MesMoOCl(3)](2)(THF)(2), which has been characterized by X-ray structural analysis. In 3 two MesMoO(3) units are linked in a ring-like manner via magnesium ions, The anion 3a, which possesses a distorted trigonal-bipyramidal arrangement, was also isolated as [Mg(THF)(6)][MesMoOCl(3)](2) which was investigated by X-ray analysis, The reaction of MoO2Cl2 with MgMes(2) in a 1:0,5 ratio generates thr compounds [Mg(THF)(4)(MoO3Cl)(2)] and MoOCl3(THF)(2). Reaction pathways which may lead to these compounds are discussed.

  DOI：

  10.1002/(sici)1521-3749(199802)624:2<322::aid-zaac322>3.3.co;2-j

文献信息

• Dioxo-molybdenum(VI) and -tungsten(VI) BINOL and alkoxide complexes: Synthesis and catalysis in sulfoxidation, olefin epoxidation and hydrosilylation of carbonyl groups
  作者：André Pontes da Costa、Patrícia M. Reis、Carla Gamelas、Carlos C. Romão、Beatriz Royo

  DOI：10.1016/j.ica.2007.10.011

  日期：2008.5

  catalyst in the sulfoxidation of methyl phenyl sulfide and in the epoxidation of cis -cyclooctene with tert -butylhydroperoxide, under mild conditions. The BINOL complex was, however, not found to be enantioselective. In addition, the catalytic activity of the molybdenum species MoO 2 ( S -BINOL)(THF) 2 and MoO 2 [OCMe(CF 3 ) 2 ] 2 (THF) in the hydrosilylation of carbonyl groups has been explored.

  摘要MoO 2（mes）2与S -H 2 BINOL（mes = 2,4,6-Me 3 C 6 H 2; H 2 BINOL = 1,1'-bi-2-萘酚）和（CF 3）2 MeCOH在THF中的生成分别为新型二氧钼（VI）络合物MoO 2（S -BINOL）（THF）2和MoO 2 [OCMe（CF 3）2] 2（THF）。通过使WO 2 Cl 2（DME）与BINOL的相应锂盐反应，可以制得相似的钨衍生物WO 2（S -BINOL）（THF）和WO 2 [OCMe（CF 3）2] 2（THF）。 1,1,1,3,3,3-六氟-2-甲基-2-丙醇 催化实验表明，在温和条件下，MoO 2（S -BINOL）（THF）2是甲基苯硫醚的硫氧化反应和顺式环辛烯与叔丁基氢过氧化物环氧化反应的活性催化剂。然而，未发现BINOL复合物是对映选择性的。此外，
• Preparation and X-ray structure determination of an aryltrioxomolybdenum(VI) anion
  作者：H. Arzoumanian、R. Lai、S. Le Bot、M. Pierrot、F. Ridouane

  DOI：10.1016/s0020-1693(00)90152-x

  日期：1991.4

  yields the mesityltrioxomolybdate (VI) anion, resulting from an oxygen atom transfer from one molybdenum atom to another. The molecular and crystal structure of the anion was determined by X-ray diffraction on the tetraphenylphosphonium salt. The structure was solved via standard heavy atom procedure, completed by subsequent difference Fourier method and refined to R =0.033 using 4300 reflections. The

  摘要在0°C下，四氢呋喃中的二乙二氧肟酸钼（VI）与亚乙基三乙氧磷烷反应生成三乙氧钼酸根（VI）阴离子，这是由于氧原子从一个钼原子转移到另一个钼原子而产生的。通过在四苯基phosph盐上的X射线衍射确定阴离子的分子和晶体结构。该结构通过标准重原子程序解析，通过随后的差分傅立叶方法完成，并使用4300次反射将其精炼为R = 0.033。晶体系统是三斜晶P 1，a = 10.523（3），b = 15.061（5），c = 10.248（3）A，α= 108.90（5），β= 97.47（5）和γ= 102.11（5） °。分子构象具有包括芳香环和一个MoO键的单一平面；这允许氧原子和甲基碳之间存在相互作用。
• Reactivity of carbon monoxide towards high valent molybdenum complexes
  作者：Richard Laï、Sylvie Le Bot、Fatiha Djafri

  DOI：10.1016/0022-328x(91)83007-q

  日期：1991.6

  metal complex. It has been shown that the relative ratio of 1 and 2 is dependent on the reaction conditions and that the presence of pyridine is essential for the formation of 1. Reactions of CO with the isoelectronic complex Mo(NtBu)2mes2 contrast sharply with Mo(O)2mes2 and, under the same conditions, no dihydropyridine is formed, the sole identified products being 1 (60%) and mesityltertiobutyl amide

  一氧化碳（3 atm）与Mo（O）2（MES）2（MES =甲基1 = C 6 H 2 Me 3 -2,4,6）在室温下在吡啶中的反应提供二甲基苯乙烯酮1（5％）和1,1'-双（间苯二甲酰基）-1,1'，4,4'-四氢-4,4'-联吡啶2（25％），其分子结构已通过X射线衍射研究确定。2的形成代表由过渡金属络合物介导的CO对吡啶进行N-酰化的第一个例子。已经表明，相对比率为1和2取决于反应条件，吡啶的存在对于1的形成是必不可少的。与等电子复杂沫（N CO的反应吨丁基）2个MES 2用的Mo（O）对比度急剧2个MES 2和，在相同条件下，无二氢形成，鞋底鉴定产物为1（60％）和MESityltertiobutyl酰胺HN（t Bu）COMES（40％）。根据实验结果以及对二氧杂和二酰亚胺d 0钼配合物进行的扩展Hückel计算，初步推测了2形成的机理。 在更亲电子的二氧杂钼物种的情况下，提出了涉及类似氧杂环戊烷的中间体的方法。
• Crystal and molecular structure of a dioxo-molybdenum phosphorus-substituted alkylidene resulting from the first observed aryl migration from molybdenum to carbon
  作者：Henri Arzoumanian、Andr� Baldy、Richard Lai、Jacques Metzger、Marie-Louise Nkeng Peh、Marcel Pierrot

  DOI：10.1039/c39850001151

  日期：——

  The reaction of Mo(O)2(mesityl)2 with Bu3PCH2 yields (mesityl)(O)2MoC(mesityl)PBu3, the first example of a dioxo-metal phosphorus-substituted carbene resulting a double α-hydrogen abstraction and aryl migration from molybdenum to carbon within the co-ordination sphere of the metal.

  Mo（O）2（mesityl）2与Bu 3 PCH 2的反应生成（mesityl）（O）2 Mo C（mesityl）PBu 3，这是二氧金属磷取代的卡宾的第一个实例，导致双α-在金属的配位范围内，氢从钼到碳的夺氢和芳基迁移。
• An unusual route to the isopolymolybdates; Octamolybdate β-[Mo8O26]4− and hexamolybdate [Mo6O19]2−. Reaction of dioxomolybdenum complexes with triphenylphosphonium ylides. Crystal structures of the salts [PPh3CH2COOEt]+2[NH2Et]+2 [Mo8O26]4−, [PPh3CH2COOEt]+2 [Mo6O19]2−, and [PPh3CH2Ph]+2 [Mo6O19]2−
  作者：Henri Arzoumanian、André Baldy、Richard Lai、América Odreman、Jacques Metzger、Marcel Pierrot

  DOI：10.1016/0022-328x(85)80318-1

  日期：1985.11

  (R = Ph, COOEt, H) in dichloromethane. The polyoxoanions are of two types, β-[Mo8O26]4− and [Mo6O19]2−, depending on the starting molybdates. X-ray structure determinations have been performed on the salts [PPh3CH2COOEt]+2 [NH2Et]+2 [Mo8O26]4−, [PPh3CH2COOEt]+2 [Mo6O19]2−, and [PPh3CH2Ph]+2 [Mo6O19]2−.

  与各种抗衡阴离子Isopolymolybdate已经从二氧合钼的反应得到（VI）化合物和三苯基鏻叶立德RCHPPh 3在二氯甲烷（R = PH，COOEt烷基，H）。取决于起始钼酸盐，聚氧阴离子为两种类型，β-[Mo 8 O 26 ] 4-和[Mo 6 O 19 ] 2-。已经对盐[PPh 3 CH 2 COOEt] + 2 [NH 2 Et] + 2 [Mo 8 O 26 ] 4-，[PPh 3CH 2 COOEt] + 2 [Mo 6 O 19 ] 2-和[PPh 3 CH 2 Ph] + 2 [Mo 6 O 19 ] 2-。