{Mo(NCMe)2(CO)2(η5-C5Me5)}{BF4} | 121987-71-1

• 英文名称: {Mo(NCMe)2(CO)2(η5-C5Me5)}{BF4}
• 英文别名: cis-Mo(CO)2(MeCN)2(η(5)-C5Me5)
• CAS: 121987-71-1
• 化学式: BF₄*C₁₆H₂₁MoN₂O₂
• 分子量: 456.1
• InChiKey: DKQTZEJIXHSLAT-UHFFFAOYSA-N

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：

  {Mo(NCMe)2(CO)2(η5-C5Me5)}{BF4} 、 1,2,3,4,5-五甲基环戊二烯 以 二氯甲烷 为溶剂， 以90%的产率得到[(C5Me5)Mo(η(4)-C5Me5H)(CO)2]BF4
  参考文献：
  名称：

  Ascenso, José R.; De Azevedo, Cristina G.; Gonçalves, Isabel S., Organometallics, 1995, vol. 14, # 8, p. 3901 - 3919

  摘要：

  DOI：
• 作为产物：
  描述：

  乙腈 、 四氟硼酸-二乙醚络合物 、 以 二氯甲烷 为溶剂， 以86%的产率得到{Mo(NCMe)2(CO)2(η5-C5Me5)}{BF4}
  参考文献：
  名称：

  Reactions of co-ordinated ligands. Part 50. The synthesis of functionalised η³-allyl complexes of molybdenum and their conversion into η⁴-s-trans-1,3-dienes

  摘要：

  Reaction of the labile bis(acetonitrile) complexes [Mo(NCMe)2(CO)2(eta-5-L)][BF4] (L = C9H7 1 or C5Me5 2) with the 1-trimethylsilyloxybuta-1,3-dienes Me3SiOCH = CR1CH = CHR2 (R1 = R2 = H; R1 = Me, R2 = H; R1 = H, R2 = Me) results in initial co-ordination of the diene followed by a rapid desilylation affording the 4-oxo-functionalised allyls [Mo(eta-3-CR2R3CHCR1CHO)(CO)2(eta-5-L)] 4 and 6-9. Complexes 4 and 6-9 are generated in the form of isomeric mixtures, arising through syn-anti isomerism at C2 of the allyl ligand together with the presence of non-interconvertible exo and endo orientations for the latter with respect to the metal fragment. Addition of Ph3P = CH2 to 6 (R1 = R2 = R3 = H) and 7 (R1 = Me, R2 = R3 = H) effects smooth conversion into the eta-3-pentadienyl complexes [Mo(eta-3-CR2R3CHCR1CHCH2)(CO)2(eta-5-C5Me5)] 11 (R1 = R2 = R3 = H) and 12 (R1 = Me, R2 = R3 = H). The low-temperature (-78-degrees-C) protonation of compounds syn-6-8 using CF3SO3H results in a quantitative transformation into the s-trans-diene cations [Mo(eta-4-s-trans-trans-HOCHCR1CHCR2R3)-(CO)2(eta-5-C5Me5)][CF3SO3] 13 (R1 = R2 = R3 = H), 14 (R1 = Me, R2 = R3 H) and 15 (R1 = R3 = H, R2 = Me), characterised in situ by H-1 NMR spectroscopy. Above -30-degrees-C, 13-15 undergo an irreversible rearrangement in solution to the corresponding s-cis diene cations. Deprotonation of 13-15 by treatment with NEt3 regenerates the syn isomers of 6-8, whilst the s-cis diene cations produce only the anti species under the same conditions. These results are interpreted in terms of an overall retention of stereochemistry of the C4 ligand throughout these manipulations. The eta-3-pentadienyl complexes 11 and 12 undergo analogous transformations upon addition of CF3SO3H producing the thermally unstable s-trans-diene cations [Mo(eta-4-s-trans-trans-MeCHCRCHCH2)(CO)2(eta-5-C5Me5)][CF3SO3] 16 (R = H) and 17 (R = Me), which are likewise converted into their s-cis isomers at temperatures in excess of -20-degrees-C.

  DOI：

  10.1039/dt9910000895

文献信息

• Synthesis and reactivity of η³-γ-lactonyl complexes of molybdenum; crystal structures of [Mo{η³-OC(O)CHCHCH}(CO)₂(η-C₅Me₅)], [Mo{η-²PhCH₂NHCHCHCH(CO₂H)}(CO)₂(η⁵-C₉H₇)] and [Mo{η³-OC(O)CHCHCHCO}(NCMe)(CO)(η-C₅H₅)]
  作者：Christopher Butters、Nicholas Carr、Robert J. Deeth、Michael Green、Simon M. Green、Mary F. Mahon

  DOI：10.1039/dt9960002299

  日期：——

  zwitterionic, η2-alkene complex [Moη2-PhCH2NHCHCHCH(CO2H}(CO)2(η5-C9H7)]. Similarly, [Moη3-[graphic omitted]H}(CO)2(η-C5H5)] and methoxide anion gives, after acidification, [Moanti-η3-(MeO)CHCHCH(CO2H)}(CO)2(η-C5H5)], in which the lactone ring has been cleaved to give an η3-allyl moiety ligating the metal centre. An extended Hückel molecular orbital calculation on [Moη3-[graphic omitted]H}(CO)2(η-C5Me5)] suggests

  与化合物2-（三甲基甲硅烷基）呋喃的反应顺- [沫（NCMe）2（CO）2 L] [BF 4 ]（L =η-C 5 H ^ 5，η-C 5我5或η 5 -C 9 ħ 7，得到η）3 -γ-内酯配合物[沫η 3 - [图形省略] H}（CO）2 L]。这些物种之一，[Mo的结构η 3 - [图形省略] H}（CO）2（η-C 5我5）]，已经通过单晶X射线衍射研究，其证实了γ-内酯部分结合到钼建立经由三个碳原子作为η 3 -烯丙基。用亲核试剂（胺，甲醇盐）处理这些内酯配合物会导致内酯环打开，并将亲核试剂整体添加到内酯环的γ-碳上，而不是如预期的那样在内酯羰基碳原子上加成。之间的反应的产物[沫η 3 - [图形省略] H}（CO）2（η 5 -C 9 ħ 7）]和的PhCH 2 NH 2已经在结构上，其特征在于X射线衍射研究的两性离子，η 2 -烯烃络合物[沫η 2 -PhCH 2 NHCHCH
• Reactions of co-ordinated ligands. Part 54. Synthesis of (1,2,3-η)-trans-butadienyl complexes by deprotonation or desilylation of cationic molybdenum 1,3-diene complexes; formation of η⁴-vinylketene complexes and crystal structures of [Mo{(1,2,3-η)-trans-CH₂CHCCH₂}(CO)₂(η-C₅Me₅)], [Mo{η³-CH₂CC(Me)CH₂CO}(CO)₂(η-C₅Me₅)] and [Mol{η⁴-CH₂CHC(Me)CO}(CO)(η-C₅Me₅)]
  作者：Stephen A. Benyunes、Robert J. Deeth、Arno Fries、Michael Green、Mary McPartlin、Caroline B. M. Nation

  DOI：10.1039/dt9920003453

  日期：——

  [NBun4]F with the cation [Moη4-CH2CHC(SiEt3)CH2}(CO)2(η-C5Me5)][BF4]. The desilylation reaction has also been used to transform [Moη4-syn-CH(Ph)CHC(SiMe3)CH2}(CO)2(η-C5Me5)][BF4] into a mixture of exo- and endo-[Mo(1,2,3-η)-trans-syn-CH(Ph)CHCCH2}(CO)2(η-C5Me5)]. An alternative synthetic route to (1,2,3-η)-trans-butadienyl complexes was explored involving reaction of Li[Mo(CO)3(η-C5Me5)] with CH2CC(Me)CH2Cl

  一个基座的Li [N（森的反应的产物的3）2 ]与[沫（η 4 -C 4 H ^ 6）（CO）2（η-C 5我5）] [BF 4 ]是外-orientated（1,2,3-η） -反式-butadienyl络合物[沫（1,2,3-η） -反式-CH 2 CHC CH 2 }（CO）2（η-C 5我5） ]。后者的单晶X射线衍射研究表明，两个相邻的π系统，烯丙基和C CH 2丁二烯片段中的α彼此正交。该复合物可以通过下述物质反应[NBU选择性和高收率形成Ñ 4 f让阳离子[沫η] 4 -CH 2 CHC（SIET 3）CH 2 }（CO）2（η-C 5我5） ] [BF 4 ]。的脱甲硅烷基反应也被用于转化[沫η 4 -顺式-CH（PH）CHC（森达3）CH 2 }（CO）2（η-C 5我5）] [BF 4 ]成的混合物exo-和内- [钼（1,2,3-η） -反式-顺式-CH（PH）CHC
• The synthesis, structure and reactivity of aldehyde substituted η3-allylic complexes of molybdenum1Dedicated to Professor Ken Wade on the occasion of his 65th birthday.1
  作者：Claire J Beddows、Matthew R Box、Christopher Butters、Nicholas Carr、Michael Green、Monika Kursawe、Mary F Mahon

  DOI：10.1016/s0022-328x(97)00542-1

  日期：1998.1

  [Moη3-exo-anti-CH2CHCHCH(OH)R}(CO)2(η5-C5H5)] [11 (R=Me), 12 (R=Et), 13 (R=Ph)]. Similarly, treatment of 2 with MeLi gave the corresponding alcohol 14. An attempt to carry out the Oppenauer oxidation [Al(OPr′)3/Me2CO] of 11 resulted in an elimination reaction and the formation of the η3-s-pentadienyl complex [Moη3-exo-anti-CH2CHCH(CHCH2)}(CO)2(η5-C5H5)], which was structurally identified by X-ray crystallography

  的反应顺- [沫（NCMe）2（CO）2（η 5 -L）] [BF 4 ]（L = C 5 H ^ 5或C 5我5）与1- acetoxybuta -1,3-二烯给出阳离子络合物[沫 η 4 -顺式-小号-顺式-CH 2 CHCHCH（OAC）}（CO）2（η 5 -L）] [BF 4 ]，其在与含水的NaHCO反应3 / CH 2氯2，提供良好的抗收率-醛取代的配合物[沫 η 3 -外型-抗- CH 2 CHCH（CHO）}（CO）2（η 5 -L）] 2（L = C 5我5），4（L = C 5 H ^ 5）]。相应的η 5 -茚基取代的复杂5的制备是通过质子化（HBF 4 ·OET 2的）的Mo（η 3 -C 3 H ^ 5）（CO）2（η 5 -C 9H 7）]，然后加入CH 2 = CHCH = CH （OAc）并水解（NaHCO 3 / CH 2 Cl 2水溶液）。配合物2
• Kuehn, Fritz E.; Herdtweck, Eberhardt; Haider, Joachim J., Journal of Organometallic Chemistry, 1999, vol. 583, p. 3 - 10
  作者：Kuehn, Fritz E.、Herdtweck, Eberhardt、Haider, Joachim J.、Herrmann, Wolfgang A.、Goncalves, Isabel S.、et al.

  DOI：——

  日期：——