(but-2-yne)(η5-cyclopentadienyl)bis(trimethyl phosphite)molybdenum tetrafluoroborate | 66593-42-8

• 英文名称: (but-2-yne)(η5-cyclopentadienyl)bis(trimethyl phosphite)molybdenum tetrafluoroborate
• 英文别名: [Mo(P(OMe)3)2(η-MeCCMe)(η-C5H5)][BF4]
• CAS: 66593-42-8
• 化学式: BF₄*C₁₅H₂₉MoO₆P₂
• 分子量: 550.084
• InChiKey: QLWPSAPVBBLPHJ-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：

  (but-2-yne)(η5-cyclopentadienyl)bis(trimethyl phosphite)molybdenum tetrafluoroborate 、 sodium tetrahydroborate 在 trimethyl phosphite 作用下， 以 四氢呋喃 为溶剂， 生成 [Mo(P(OCH3)3)2(η3-anti-1-CH3C3H4)(η-C5H5)]
  参考文献：
  名称：

  Allen, Stephen R.; Baker, Paul K.; Barnes, Stephen G., Journal of the Chemical Society, Dalton Transactions, 1983, p. 927 - 940

  摘要：

  DOI：
• 作为产物：
  描述：

  bis(but-2-yne)carbonyl(η5-cyclopentadienyl)molybdenum tetrafluoroborate 、 三甲氧基磷 以 二氯甲烷 为溶剂， 以89%的产率得到(but-2-yne)(η5-cyclopentadienyl)bis(trimethyl phosphite)molybdenum tetrafluoroborate
  参考文献：
  名称：

  配位体的反应。17.部分的合成和反应的阳离子η 5 -indenyl-和含有1,3-二烯和乙炔配体η环戊二烯基钼配合物

  摘要：

  的反应[{沫（CO）3（η 5 -C 9 ħ 7）} 2 ]有Ag [BF 4 ]在MeCN得到[沫（CO）2（NCMe）2（η 5 -C 9 ħ 7）] [BF 4 ]，与L = P（OMe）3，Ph 2 PCH 2 CH 2 PPh 2，丁1,3-二烯，异戊二烯，2,3，-二甲基丁-1,3-二烯或反式反应-戊-1,3，二烯形式[沫（CO）2大号2（η 5 -C 9 ħ 7）] [BF 4 ]; 备选地，1,3-二烯络合物，包括那些环己-1,3-的，二烯和环octatetraene，可直接从形成[{沫（CO）3（η 5 -C 9 ħ 7）} 2 ] ，Ag [BF 4 ]和1，3-二烯。钠的反应[BH 4 ]或1- morpholinocyclopent -1-烯与所述的区域选择性形成1,3-二烯阳离子结果抗-取代的η 3 -烯丙基配合物。[沫（CO）的治疗2（NCMe）2（η 5 -C

  DOI：

  10.1039/dt9770002365

文献信息

• Reactions of co-ordinated ligands. Part 32. The reaction of sulphur nucleophiles with cationic molybdenum alkyne complexes: alkyne rotation and the molecular structures of the complexes [Mo(SC₆H₄NO₂-p){P(OMe)₃}(η²-MeC₂Me)(η-C₅H₅)] and [Mo(SC₆H₄SPh-o)(CO)(η²-MeC₂Me)(η-C₅H₅)]
  作者：Stephen R. Allen、Timothy H. Glauert、Michael Green、Kevin A. Mead、Nicholas C. Norman、A. Guy Orpen、Colin J. Schaverien、Peter Woodward

  DOI：10.1039/dt9840002747

  日期：——

  Treatment of [MoP(OMe)3}2(η2-MeC2Me)(η-C5H5)][BF4] with NaSR (R = Me, p-NH2C6H4, p-MeOC6H4, p-MeC6H4, C6H5, or p-NO2C6H4) leads to displacement of P(OMe)3 and formation of [Mo(SR)P(OMe)3}(η2-MeC2Me)(η-C5H5)]. Similar reactions afforded [Mo(SePh)P(OMe)3}-(η2-MeC2Me)(η-C5H5)] and [Mo(SMe)P(OMe)3}(η2-ButC2H)(η-C5H5)]. Barriers to rotation of the but-2-yne ligand present in these complexes are related to electronic

  [沫P（OME）的治疗3 } 2（η 2 -MeC 2 Me）的（η-C 5 H ^ 5）] [BF 4 ]与纳斯尔（R = Me中，p -NH 2 ç 6 ħ 4，p -MeOC 6 H 4，p -MeC 6 H 4，C 6 H 5或p -NO 2 C 6 H 4）导致P（OMe）3置换并形成[Mo（SR）P（OMe）3 }（η2 -MeC 2 Me）的（η-C 5 H ^ 5）]。类似的反应，得到[沫（SEPH）P（OME） 3 } - （η 2 -MeC 2 Me）的（η-C 5 H ^ 5）]和[沫（SME）P（OME） 3 }（η 2 -卜吨ç 2 H）（η-C 5 H ^ 5）]。这些配合物中丁-2-炔配体的旋转障碍与硫醇盐配体上取代基的电子效应有关。[Mo（SC 6 H 4 NO 2 - p）P（OMe） 3 }（η2 -MeC 2 Me）的- （η-C 5 H ^
• Reactions of co-ordinated ligands. Part 24. The reaction of bis-(but-2-yne)carbonyl(η-cyclopentadienyl or η⁵-indenyl)molybdenum tetrafluoroborate with acetonitrile and phosphines; crystal structures of but-2-ynecarbonyl(η⁵-indenyl)(triethylphosphine)molybdenum tetrafluoroborate and but-2-yne(η⁵-indenyl)bis(trimethylphosphine)molybdenum tetrafluoroborate
  作者：Stephen R. Allen、Paul K. Baker、Stephen G. Barnes、Michael Green、Lynda Trollope、Ljubica Manojlović-Muir、Kenneth W. Muir

  DOI：10.1039/dt9810000873

  日期：——

  η-5-C9H7)][BF4]. X-Ray single-crystal crystallographic studies were carried out on the compounds [Mo(CO)(PEt3)(MeC2Me)(η5-C9H7)][BF4] and [Mo(PMe3)2(MeC2Me)(η5-C9H7)][BF4]. Crystals of the former are monoclinic, space group P21/c, Z= 4, in a unit cell of dimensions a= 9.158(2), b= 14.726(2), c= 16.581(3)Å, and β= 94.12(2)°. Crystals of the latter complex are also monoclinic, space group P21, Z= 2, in a

  的化合物的反应[沫（CO）（RC 2 - [R 1）2（η-C 5 H ^ 5或η 5 -C 9 ħ 7）] [BF 4 ]与在相应的乙炔的存在下回流的乙腈，得到的化合物[沫（NCMe）（RC 2 - [R 1）2（η-C 5 H ^ 5或η 5 -C 9 ħ 7）] [BF 4 ]，其中R = R 1 =甲基; R = Bu t，R 1 = H；R = Ph，R 1 = Me；R = Pr 1，R 1 = H。的治疗[沫（CO）（RC 2 - [R 1）2（η-C 5 H ^ 5或η 5 -C 9 ħ 7）] [BF 4 ]在二氯甲烷中室温下用PET 3，PPH 3，或P（C 6 H ^ 11）3给出了monoacetylene化合物[沫（CO）L（RC 2 - [R 1）（η-C 5 H ^ 5或η 5 -C 9 ħ 7）] [BF 4 ] [L = PEt 3，PPh3，P（C 6 H
• Thiolates vs. halides as π-donors: the redox-active alkyne complexes [M(SR)L(η-R′CCR′)L′] {M = Mo or W, L = CO or P(OMe)3, L′ = η-C5H5 and Tp′}
  作者：Christopher J. Adams、Angharad Baber、Supakorn Boonyuen、Neil G. Connelly、Beatriz E. Diosdado、Anob Kantacha、A. Guy Orpen、Elena Patrón

  DOI：10.1039/b912986c

  日期：——

  alkyne complexes [M(SR)L(eta-R'C[triple bond, length as m-dash]CR')(eta-C(5)H(5))] (M = Mo or W, R = Me or Ph, R' = Me or Ph) show two oxidation processes. Both are irreversible for the stereochemically rigid carbonyls (L = CO) but the first is reversible for the fluxional phosphites L = P(OMe)(3)}; the paramagnetic monocations [M(SPh)P(OMe)(3)}(eta-MeC[triple bond, length as m-dash]CMe)(eta-C(5)H(5))](+)

  炔烃配合物的循环伏安图[M（SR）L（eta-R'C [三键，长度为m-破折号CR'）（eta-C（5）H（5））]（M = Mo或W，R = Me或Ph，R'= Me或Ph）显示出两个氧化过程。两者对于立体化学上刚性的羰基（L = CO）都是不可逆的，但是对于通量亚磷酸酯来说，第一个是可逆的L = P（OMe）（3）}; 顺磁性单阳离子[M（SPh）P（OMe）（3）}（eta-MeC [三键，长度为m-破折号CMe）（eta-C（5）H（5））]（+）为原位化学单电子氧化后，通过ESR光谱检测到。相比之下，氢三（吡唑基）硼酸酯类似物[W（SR）（CO）（eta-PhC [三键，长度为m-dash] CPh）Tp'] R = Me或Ph，Tp'= hydrotris（3 （5-甲基吡唑基）硼酸酯}在两个可逆步骤中被氧化为相应的一元和二元化合物；氧化还原对[W（SPh）（CO）（eta-PhC
• Reaction of the η²(4e)-donor alkyne complexes [Mo{η²(4e)-R¹C₂R²}{P(OMe)₃}₂(η-C₅H₅)](R¹= R²= Ph or Me; R¹= Me, R²= Ph) with the Grignard reagents MgR³(X)(R³= Me, Et, CH₂Ph, CH₂CHCH₂or CHCH₂) and CH₂(MgI)₂
  作者：Georg Brauers、Frank J. Feher、Michael Green、John K. Hogg、A. Guy Orpen

  DOI：10.1039/dt9960003387

  日期：——

  Reaction of the complex [Moeta(2)(4e)-PhC(2)Ph}P(OMe)(3)}(2)(eta-C5H5)][BF4]1 with MgR(X) (R = Me, Et or PhCH(2)) afforded good yields of [Moeta(2)(4e)-PhC(2)Ph}RP(OMe)(3)}(eta-C5H5)]. Unexpectedly, reaction of 1 with the 1,1-di-Grignard reagent CH2(MgI)(2) gave the X-ray crystallographically identified zwitterionic complex [Moeta(2)(4e)-PhC(2)Ph}eta(2)-P(OMe)(2)OBF2OP(OMe)(2)}(eta-C5H5)], similar reactions with the but-2-yne and 1-phenylprop-2-yne complexes affording the analogous [Moeta(2)(4e)-RC(2)R(2))eta(2)-P(OMe)(2)OBF2OP(OMe)(2)}(eta-C5H5)] (R = R(2) = Me; R = Me, R(2) = Ph). Treatment of the zwitterionic diphenylacetylene- and 1-phenylprop-2-yne-substituted complexes with K[BHBu(3)(s)] gave the anionic eta(2)(3e)-vinyl complexes K[Mo=C(R)CH(Ph)}eta(2)-P(OMe)(2)OBF2OP(OMe)(2)(eta-C5H5)] (R = Ph or Me). Protonation (HBF4 . Et(2)O) of the diphenyl-substituted eta(2)(3e)-vinyl complex followed by addition of carbon monoxide, trimethyl phosphite, or diphenylacetylene afforded trans-stilbene and the complexes [Mo(CO)(2)eta(2)-P(OMe)(2)OBF2OP(OMe)(2)}(eta(2)-C5H5)], [MoP(OMe)(3)}(2)eta(2)-P(OMe)(2)OBF2OP(OMe)(2)}(eta-C5H5)] and [Moeta(2)(4e)-PhC(2)Ph}eta(2)P(OMe)(2)OBF2OP(OMe)(2)}(eta-C5H5)] respectively. When CH2=CHCH2MgBr was added to 1 an unstable compound was formed, which on addition of P(OMe)(3) gave [Moeta(3)-C(Ph)=C(Ph)CH2CH=CH2}P(OMe)(3)}(2)(eta-C5H5)], the identity of which was confirmed by X-ray crystallography. This reaction is explained in terms of an unusual metalla-3,3-sigmatropic shift process. A similar reaction between 1 and CH2=CHMgBr followed by addition of P(OMe)(3) surprisingly gave the eta(3)-cyclopropenyl complex [Mo(eta(3)-C(3)Ph(2)Me)P(OMe)(3)}(2)(eta-C5H5)]. The complex [Moeta(2)(4e)-PhC(2)Ph}MeP(OMe)(3)}(eta-C5H5)] reacted thermally (78 degrees C) with an excess of PhC(2)Ph to give the X-ray crystallographically identified complex [MoH(eta(4)-C(5)H(2)Ph(4))P(OMe)(3)}(eta-C5H5)], which on heating (100 degrees C) afforded the dihydride [MoH2(eta(5)-C(5)HPh(4))(eta-C5H5)].