[Mo2Cp2(μ-SMe)3(xylNC)2](BF4) | 870539-78-9

• 英文名称: [Mo2Cp2(μ-SMe)3(xylNC)2](BF4)
• 英文别名: [Mo2(η5-cyclopentadienyl)2(μ-SMe)3(2,6-xylyl isocyanide)2]
• CAS: 870539-78-9
• 化学式: BF₄*C₃₁H₃₇Mo₂N₂S₃
• 分子量: 812.531
• InChiKey: RRSAQQNNWBEVBR-UHFFFAOYSA-K

反应信息

• 作为反应物：
  描述：

  [Mo2Cp2(μ-SMe)3(xylNC)2](BF4) 在 NaOH 作用下， 以 四氢呋喃 为溶剂， 以84%的产率得到[Mo2Cp(μ-SMe)3(μ-(η5-C5H4)(xylN)CN(xyl)C)]
  参考文献：
  名称：

  Formation of C−C, C−N, and C−O Links between Isonitrile, Cyclopentadienyl, and Hydroxide Ligands Bound to Molybdenum(III):  Syntheses and Crystal Structures of μ-Aminocarbyne and μ-Amino-oxycarbene Dimolybdenum Complexes

  摘要：

  Reaction of the bis- isonitrile complex [Mo2Cp2(mu-SMe)(3)(xylNC)(2)](BF4) (2b) with NaOH (suspension) under reflux in tetrahydrofuran produced, in quantitative yields, the A-alkylidyne species [Mo2Cp(mu-SMe) (3){mu-(5-C5H4)(xylN)CN(xyl)C}] (4), in which a deprotonated Cp and both isonitrile ligands of 2b are now linked by new C-C and C-N bonds. Under prolonged reflux (72 h) in tetrahydrofuran 2b with either NaOH (suspension) or (Me4N) OH (in MeOH) in the presence of excess isonitrile RNC (R = xyl, Bu-t) was converted in high yields into the mixed (mu-alkylidyne)(mu-amino-oxycarbene) derivatives [Mo2Cp(mu-SMe)(2){mu-(eta(5)-C5H4)(xylN)CN(xyl)C}{mu-eta(1)(O),eta(1)(C)-OCNHR}] (R = xyl (5a1), R = Bu-t (5b2)) and [Mo2Cp(mu-SMe)(2){mu-(eta(C5H4)-C-5)(xylN)CN(xyl)C}{mu-eta(1)(O),eta(1)(C)-OCNMeR}] (R = xyl (6a)). All these products result from hydroxide-isonitrile coupling reactions. When the mixture of 2b, (Me4N) OH (excess), and ButNC (excess) in tetrahydrofuran was heated under reflux for a short time (2 h), complex 5b1 was formed in good yields. Compounds 5b1 and 5b2 are linkage isomers, which differ only in the mode of coordination of the mu-amino-oxycarbene ligand to the Mo1-Mo2 unit; 5b1 converts into 5b2 on prolonged heating. Reaction of the secondary amino-oxycarbene derivative 5a1 with a base (NaOH) and an alkylating agent R"4NBr (R" = Et, Bu-n) afforded the corresponding tertiary(amino)-oxycarbene complexes [Mo2Cp(mu-SMe)(2){mu-(eta(5)-C5H4)(xylN)CN(xyl)C}{mu-eta(1)(O),eta(1)(C)-OCNxylR"}] [R" = Et (6b), Bu-n (6c)]. On heating a tetrahydrofuran solution of the mu-alkylidyne compound 4 with NaOH (suspension) and an excess of either xylNC or (BuNC)-N-t, the mixed mu-alkylidyne and mu-amino-oxycarbene species 5a1 and 5b2 were obtained, demonstrating that 4 is an intermediate in the formation of 5a1 and 5b2 from 2b. Treatment of the mixed isonitrile-nitrile species [Mo2Cp2(mu-SMe)(3)(MeCN)(xylNC)](BF4) (3), containing a labile MeCN group, under reflux in tetrahydrofuran with NaOH (suspension) afforded quantitatively the mu-aminooxycarbene compound [Mo2Cp2(mu-SMe)(3){mu-eta(1)(O),eta(1)(C)-OCNHxyl}] (7). All new complexes have been characterized by elemental analyses and spectroscopic methods, supplemented for 5a1, 5b1, 5b2, 6a, 6b, and 7 by X-ray diffraction studies.

  DOI：

  10.1021/om060383v
• 作为产物：
  描述：

  四氟硼酸-二乙醚络合物 、 [Mo2(η5-cyclopentadienyl)2(μ-SMe)3(μ-η1:η1-C(NHC6H3Me2)CNC6H3Me2)] 以 二氯甲烷 为溶剂， 以86%的产率得到[Mo2Cp2(μ-SMe)3(xylNC)2](BF4)
  参考文献：
  名称：

  C-C，C-S，和C-N偶联与脱烷基化进程中的阳离子的Tris（thiolato）dimolybdenum（III）配合物[沫2的Cp 2（μ-SME）3大号2 ] +（L = xylNC，吨- BuNC，CO，MeCN）

  摘要：

  在双连接于相邻的钼原子（芳基胩）络合物[沫胩配体之间的还原偶合2的Cp 2（μ-SME）3（xylNC）2 ]（BF 4）（1）通过加入硫氢化阴离子引发（ HS - ），以1在回流下在四氢呋喃中，得到，在几乎定量的产率，所述dimetallaimidoyl（氨基）卡宾衍生物[沫2的Cp 2（μ-SME）3 {μ-η 1（ç）：η 1（ç） - C（NHxyl）C（Nxyl）}]（7），其中两个异氰酸酯基现在通过新的C-C键链接1。当先前反应在大量过量的氢硫化物（20当量）的存在下，类似的实验条件下进行的，所述dithiocarbonimidate化合物[沫2的Cp 2（μ-SME）2（μ-S 2 CNxyl）]（8）以定量产率获得。该产物由随后的硫醇盐交换和取代反应产生，以提供四重硫桥连的中间体，然后将游离的异腈加成至硫代S原子上。用HBF 4处理偶联的异氰化物衍生物7仅导致形成起始配合物

  DOI：

  10.1021/om8003702