bis(acetonitrile)decacarbonyltriosmium | 871132-66-0

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: bis(acetonitrile)decacarbonyltriosmium
• 英文别名: Os₃(CO)₁₀(NCCH₃)₂；Os3(CO)10(NCMe)2；Os₃(CO)₁₀(MeCN)₂；acetonitrile;carbon monoxide;osmium
• CAS: 871132-66-0
• 化学式: C₁₄H₆N₂O₁₀Os₃
• 分子量: 932.809
• InChiKey: ZNZSHNUFLPXIMC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.68
• 重原子数：
  29
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  57.6
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  bis(acetonitrile)decacarbonyltriosmium 在 H₂O 作用下， 以 四氢呋喃 为溶剂， 生成 decacarbonyl-1κ(4)C,2κ(3)C,3κ(3)C-μ-hydrido-2:3κ(2)H-μ-hydroxy-2:3κ(2)O-trisosmium-(3 Os-Os)
  参考文献：
  名称：

  合成，表征和X射线的晶体结构（μ-H）2 O的3（CO）9（μ 3 -Te）

  摘要：

  化合物（μ-H）2 O的3（CO）9（μ 3 -Te）已经由Os制备3（CO）10 - （NCCH 3）2和H 2 Te，且其结构已经通过X-确定射线晶体学。

  DOI：

  10.1016/0022-328x(89)85404-x
• 作为产物：
  描述：

  十二羰基三锇 在 CH₃CN 、 (CH₃)3NO 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 生成 bis(acetonitrile)decacarbonyltriosmium
  参考文献：
  名称：

  os簇与1-羟基苯并三唑反应的新型NN-氧化物配合物

  摘要：

  Reaction of Os3(CO)10(NCMe)2 (1) with 1-hydroxybenzotriazole (2) gave the hydrido complex (mu-H)Os3(CO)10(mu2-(2,3-eta2)-NNN(O)C6H4) (3) in 60% yield; reaction of isocyanide complexes Os3(CO)10(CNR)(NCMe) (4: R = n-Pr, CH2Ph) with 2 gave the bridging aminocarbyne products Os3(CO)10(mu2-(2,3-eta2)-NNN(O)C6H4)(mu2-eta1-C=NHR) (5 and 6). The O-H bond of the hydroxybenzotriazole ligand was cleaved in these reactions to afford complexes 3, 5, and 6, which contained an N-oxide moiety. Complexes 5a and 6a as well as 5b and Ob were regioisomers because of the restricted rotation about the C=N double bond in the bridging aminocarbyne. These isomers exhibited different polarities and were separated by chromatography. Results-from single-crystal X-ray diffraction analyses for 3, 5a, and 6b revealed the following data. 3: P2(1)/c; a = 8.629(l) angstrom, b = 9.919(l) angstrom, c = 25.446(2) angstrom; beta = 95.447(9)-degrees, V = 21681(3) angstrom3, Z = 4, R = 2.7%, R(w) = 3.0%. 5a: P2(1)/c; a = 10.4824(6) angstrom, b = 15.76.5(2) angstrom, c = 16.001(3) angstrom; beta = 97.981(9)-degrees, V = 2618.6(6) angstrom3, Z = 4, R = 3.0%, R(w) = 3.7%. 6b: P2(1)/c; a = 9.997(2) angstrom, b = 23.639(4) angstrom, c = 12.636(2) angstrom; beta = 111.37(l)-degrees, V 2780.8(8) angstrom3, Z = 4, R = 2.9%, R(w) = 3.1%. Studies on the structures of 5a and 6b by X-ray methods provided the first evidence indicating the existence of regioisomers with different orientations of the coordinated aminocarbyne group.

  DOI：

  10.1021/om00020a033

文献信息

• Orientational isomerism in bridging 2-pyridyl complexes: orthometallation of (S )-nicotine and (R)-1-(4-pyridyl)ethanol in triosmium clusters
  作者：Antony J. Deeming、Marc J. Stchedroff、Caroline Whittaker、Alejandro J. Arce、Ysaura De Sanctis、Jonathan W. Steed

  DOI：10.1039/a902061f

  日期：——

  Diastereomeric orthometallated products, formed by treating [Os3(CO)10(MeCN)2] with (S)-nicotine or (R)-1-(4-pyridyl)ethanol, have been partially separated by TLC but completely so by HPLC. The two diastereomers of [Os3(µ-H)µ-(R)-NC5H3CH(OH)Me-4}(CO)10] 1 and 2 and four isomers of [Os3(µ-H)µ-(S)-NC5H3C4H7NMe}(CO)10], 3 to 6, two diastereomers each for the products of metallation at the 2 and 6 positions respectively, have been separated and characterized by circular dichroism (CD) spectra to obtain their relative configurations. The CD spectra in the 230–500 nm wavelength range are totally characteristic of the configuration of the Os3CN group at atoms. A crystal structure determination for isomer 2 has allowed absolute configurations of all isomers to be established. There is little enantioselection in the orthometallation process and no detectable interconversion of isomers. The compound [Os3(µ-H)2µ-(S)-NC5H3C4H7NMe}2(CO)8] was also obtained as a complex isomeric mixture which was not separated.

  通过[Os3(CO)10(MeCN)2]与(S)-烟碱或(R)-1-(4-吡啶基)乙醇反应形成的非对映异构正交金属化产物，部分通过TLC分离，但完全通过HPLC分离。[Os3(µ-H)µ-(R)-NC5H3CH(OH)Me-4}(CO)10]的两种非对映异构体1和2，以及[Os3(µ-H)µ-(S)-NC5H3C4H7NMe}(CO)10]的四种异构体3至6，分别在2和6位置金属化的产物各有两种非对映异构体，已通过圆二色谱(CD)分离和表征，以获得它们的相对构型。在230–500 nm波长范围内的CD光谱完全表征了Os3CN基团在原子上的构型。对异构体2的晶体结构测定使得所有异构体的绝对构型得以确定。在正交金属化过程中几乎没有对映选择性，也没有检测到异构体的相互转换。化合物[Os3(µ-H)2µ-(S)-NC5H3C4H7NMe}2(CO)8]也作为一个复杂的异构体混合物获得，但未被分离。
• Synthesis and characterization of new thioether derivatives of [Os3(CO)12] and [H2Os3(CO)10]; crystal and molecular structures of [Os3(CO)11(L)] [Et2S, Pr2S, S(CH2)5] and [Os3(CO)9(μ-H)(μ-X){SMe(Bu )}] (X=H, OH)
  作者：Nitsa K. Kiriakidou-Kazemifar、Eike Kretzschmar、Håkan Carlsson、Magda Monari、Simona Selva、Ebbe Nordlander

  DOI：10.1016/s0022-328x(01)00643-x

  日期：2001.3

  clusters, viz. [Os3(μ-H)(CO)10(μ-η2-C6H4SR)] and [Os3(μ-H)(CO)9(μ3-C6H4SPh)]. The similar reaction of [Os3(μ-H)2(CO)10] with Pr2S, MeSBut, MeSPh or Ph2S does not lead to discernable products except when carried out in the presence of trimethylamine N-oxide, which leads to clusters of the general formula [Os3(CO)9(μ-H)2(thioether)]. The crystal and molecular structures of [Os3(CO)11(L)] (L=Et2S, Pr2S

  [Os 3（CO）11（NCMe）]与R 2 S（R = Et，n Pr）和MeSBu t的反应导致形成[Os 3（CO）11（L）]（L =硫醚）簇其中硫醚在tri框架的赤道位置配位。当[Os 3（CO）10（NCMe）2 ]与R 2 S（R = Et，n Pr）反应时，也会形成这种单取代的簇，而同一簇与Ph 2 S或MeSPh的反应导致形成正金属簇，即。[Os 3（μ-H）（CO）10（μ-η2 -C 6 H ^ 4 SR）]和[O的3（μ-H）（CO）9（μ 3 -C 6 ħ 4 SPH）]。[Os 3（μ-H）2（CO）10 ]与Pr 2 S，MeSBu t，MeSPh或Ph 2 S的相似反应不会导致可分辨的产物，除非在三甲胺N-氧化物存在下进行，生成具有通式[Os 3（CO）9（μ-H）2（硫醚）]的簇。[Os 3（CO）11（L）]的晶体和分子结构（L = Et给出了2 S，Pr
• Oxidative addition of 1,3-diynes at triosmium clusters with cleavage of the central carbon–carbon bond: X-ray crystal structure of [Os₃(µ₃,η²-C₂Ph)(µ-C₂Ph)(CO)₉] derived from 1,4-diphenylbuta-1,3-diyne
  作者：Antony J. Deeming、Mark S. B. Felix、Paul A. Bates、Michael B. Hursthouse

  DOI：10.1039/c39870000461

  日期：——

  The diyne clusters [Os3(µ3,η2-RCCCCR)(CO)10](R = Me, Et, Ph, But, SiMe3) in hydrocarbon solvent at 120 °C decarbonylate to give the nonacarbonyl clusters [Os3(µ3,η2-C2R)(µ-C2R)(CO)9] when R = Ph, But, or SiMe3, [Os3H(µ3,σ,η2,η2-EtCC–CCCHMe)(CO)9] when R = Et, and [Os3(C4Me2)(CO)9] of known structure when R = Me; the µ-C2Ph ligand in [Os3(µ3, η2-C2Ph)(µ-C2Ph)(CO)9](X-ray structure) is unusual in bridging

  的二炔簇[O的3（μ 3，η 2 -RC CC CR）（CO）10 ]（R =甲基，乙基，PH，卜吨，森达3）中在120℃下脱羰烃溶剂，得到nonacarbonyl簇[O的3（μ 3，η 2 -C 2 R）（μ-C 2 R）（CO）9 ]当R = PH，卜吨，或森达3，[O的3 H（μ 3，σ，η 2，η 2 -EtC C-C ç CHME）（CO）9 ]当R =的Et和[O的3当R ＝ Me时，具有已知结构的（C 4 Me 2）（CO）9 ]；的μ-C 2在pH为配体[O的3（μ 3，η 2 -C 2 PH）（μ-C 2 PH）（CO）9 ]（X射线结构）是不对称桥接异常仅通过一个碳原子。
• Substitution effects at bridging vinyl ligands: Molecular structures of [Os3H(CHCHR)(CO)10] where R = OEt or ferrocenyl
  作者：Antony J. Deeming、Mark S.B. Felix、Didier Nuel、Nicholas I. Powell、Derek A. Tocher、Kenneth I. Hardcastle

  DOI：10.1016/0022-328x(90)87065-l

  日期：1990.2

  insertion of ethyl ethynyl ether (CHCOEt) into [Os3H2(CO)10] and the second by oxidative addition of ethynylferrocene (CH2 = CHFc) to [Os3(CO)10(MeCN)2] respectively. Spectroscopically both compounds are similar to known related compounds with alkyl- or aryl-substituted vinyl ligands. A single-crystal X-ray structural study of each was made in an attempt to detect any structural effects of π-donation

  两种相关化合物[O的3 H（μ，η 2 -反式-CHCHR）（CO）10 ]（R = OET或二茂铁基Ç 5 ħ 4的FeCl 5 ħ 5，FC），已经制备，首先由将乙乙炔醚（CH = COEt）插入[Os 3 H 2（CO）10 ]，然后第二次通过将乙炔基二茂铁（CH 2 = CHFc）氧化添加到[Os 3（CO）10（MeCN）2] 分别。在光谱上，这两种化合物与具有烷基或芳基取代的乙烯基配体的已知相关化合物相似。进行了每种材料的单晶X射线结构研究，以试图检测乙烯基上的取代基对π给予的任何结构影响，例如[Os 3 H（CHCHNEt 2）（CO）10 ]。后者化合物已显示出具有两性离子结构具有两个锇原子而不是正常的μ之间的亚烷基桥，η 2 bondiong的乙烯基模式。这里所研究的两种化合物具有基本上正常μ，η 2 -乙烯基桥梁，但具有朝向亚烷基键合型有些失真，更明显对于R = OET。
• New triosmium metal clusters derived from the reactions between [Os3(CO)10(NCMe)2] and amides
  作者：Timothy I. Odiaka

  DOI：10.1016/0022-328x(85)80014-0

  日期：1985.3

  Triosmium clusters of the type [Os3(CO)10(μ-H)(NHCOR)] (1; R = H, Me, Ph, Et or Pr) are formed in high yields form the reaction of [Os3(CO)10(NCMe)2] (2) with amides. The nature of the products formed from thermolysis of 1 depend on the group, R.

  的类型的Triosmium簇[O的3（CO）10（μ-H）（NHCOR）]（1 ; R = H，Me中，pH值，的Et或Pr）以高产率形成的形成[O的反应3（CO ）10（NCMe）2 ]（2）与酰胺。由1的热分解形成的产物的性质取决于基团R.