Carbon monoxide;1-isocyanopropane;osmium | 138957-26-3

• 英文名称: Carbon monoxide;1-isocyanopropane;osmium
• CAS: 138957-26-3；150407-74-2
• 化学式: C₁₅H₇NO₁₁Os₃
• 分子量: 947.821
• InChiKey: NCRFYNVKOYCXAU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  30
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  15.4
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  Carbon monoxide;1-isocyanopropane;osmium 以 二氯甲烷 、 乙腈 为溶剂， 生成 Os3(CO)9(CNPr){μ-bis(diphenylphosphino)methane}
  参考文献：
  名称：

  Lu, Kuang-Lieh; Chen, Haw-Jye; Lu, Po-Yen, Organometallics, 1994, vol. 13, # 2, p. 585 - 592

  摘要：

  DOI：
• 作为产物：
  描述：

  十二羰基三锇 、 (C6H5)3PN(n-C3H7) 以 二氯甲烷 为溶剂， 以92%的产率得到Carbon monoxide;1-isocyanopropane;osmium
  参考文献：
  名称：

  cluster簇配位域中异氰酸酯配体的转化。iso异氰化物络合物与胺的反应

  摘要：

  The osmium isocyanide complexes Os3-(CO)11(CNR) (1), synthesized from Os3(CO)12 and phosphine imides (Ph3P = NR), react with primary amines to afford the carboxamido complexes Os3(CO)10(mu(2)-CONHR')(mu(2)-C = NHR) (2) with a bridging aminocarbyne. The latter react with excess corresponding amines to yield Os3(CO)9(NH2R')(mu(2)-CONHR')(mu(2)-C = NHR) (3), which when passed through silica gel transform to produce the hydrido complexes (mu-H)Os3(CO)9(mu(2)-CONHR')(CNR) (4) with the regeneration of the isocyanide ligand. The transformation of the isocyanide ligand with the cleavage and formation of an Os-Os bond may play an important role in mediating the reactivity of the osmium cluster.

  DOI：

  10.1021/om00040a008

文献信息

• Mechanistic study of the reaction of Os3(CO)10(CNPr)(NCMe) with Brønsted acid
  作者：Chi-Jung Su、Min-Ling Chung、Han-Mou Gau、Yuh-Sheng Wen、Kuang-Lieh Lu

  DOI：10.1016/0022-328x(93)80436-f

  日期：1993.9

  The reaction of Os3(CO)10(CNPr)(NCMe) (1) with Brønsted acid in CH2Cl2 takes place initially via the protonation of 1 to yield the hydrido complex [(μ-H)Os3(CO)10(CNPr)(NCMe)]+ (2), followed by substitution of labile acetonitrile ligand with carboxylate anion to form the monodentate carboxylate complexes (μ-H)Os3(CO)10(CNPr)(η1-OCOR) (3). Spectroscopic and crystallographic evidence is presented to

  Os 3（CO）10（CNPr）（NCMe）（1）与布朗斯台德酸在CH 2 Cl 2中的反应首先通过1的质子化反应生成氢化物络合物[（μ-H）Os 3（CO）10（CNPr）（NCMe）] +（2），然后用羧酸根阴离子的不稳定乙腈配体取代，以形成单齿羧酸酯络合物（μ-H）O的3（CO）10（CNPr）（η 1 -OCOR）（3）。提供了光谱学和晶体学证据来解释该反应的机理细节。（μ-H）Os的分子结构3（CO）10（CNPr）（η 1 -OCOCF 3）（图3a）和（μ-H）O的3（CO）10（CNPr）（η 1 -OCOCCH）（图3b）已被X-确定射线衍射研究。晶体数据：3a：P 2 1；a = 11.6632（19），b = 14.7827（24），c = 14.487（3）Å; β= 103.635（15）°，V = 2427.4（7）3，Ž = 4，- [R = 5.2％，- [R瓦特=
• Reactions of 1-Hydroxypyridine-2-thione with Triosmium Clusters. Preparation and Transformation of <i>N</i>-Oxide-Containing Osmium Complexes
  作者：Jui-Te Hung、Sudalaiandi Kumaresan、Li-Chun Lin、Yuh-Sheng Wen、Ling-Kang Liu、Kuang-Lieh Lu、Jih Ru Hwu

  DOI：10.1021/om9601763

  日期：1996.12.24

  The reaction of 1-hydroxypyridine-2-thione with Os3(CO)11(NCMe) has yielded three new complexes Os3(CO)10(μ-H)(μ-η1-S-C5H4N(O)) (1, 11% yield), Os3(CO)10(μ-H)(η2-S-C5H4N(O)) (2, 16% yield), and Os3(CO)9(μ-H)(μ-η2:η1-SC5H4N(O)) (3, 3% yield). Similarly, treatment of complex Os3(CO)10(NCMe)2 with this ligand has produced the major complexes 1 and trace of 3. Prolonging the above two reactions increased

  1羟基吡啶-2-硫酮用的反应锇3（CO）11（NCMe）已经产生了三个新的配合物O的3（CO）10（μ-H）（μ-η 1 -SC 5 ħ 4 N（O） ）（1，11％产率），锇3（CO）10（μ-H）（η 2 -SC 5 ħ 4 N（O））（2，16％产率），和Os 3（CO）9（μ -H）（μ-η 2：η 1 -SC 5 ħ 4 N（O））（3，3％产率）。同样，处理复杂的Os 3具有该配体的（CO）10（NCMe）2产生了主要配合物1和3的痕量。延长上述两个反应可增加3的收率。用异氰酸tri配合物Os 3（CO）10（CNR）（NCMe）（a，R = CH 2 Ph; b，R = Pr）处理1-羟基吡啶-2-硫酮导致Os 3（CO ）9（μ-H）（CNR）（η 2 -SC 5 ħ 4 N（O））（4），锇3（CO）10（μ-η 1 -CNHCH 2 PH）（μ-η 1 -SC 5 ħ 4
• Regioselective addition of an alkyne to both CO and CNPr functionalities in osmium clusters
  作者：Jian-Yuan Huang、Kuan-Jiun Lin、Kai-Ming Chi、Kuang-Lieh Lu

  DOI：10.1039/a606815d

  日期：——

  Reaction of [Os 3 (CO) 10 (CNPr)(NCMe)] with methyl propiolate at 0 °C gave [Os 2 (CO) 6 µ-η 2 :η 3 -C(OH)C(CO 2 Me)CHCNHPr}] as the major product and [Os 2 (CO) 6 µ-η 2 :η 3 -C(OH)CHC(CO 2 Me)CNHPr}] as the minor product, in which two kinds of C–C bond formations occur regioselectively involving coupling of alkyne and CO as well as coupling of alkyne and CNPr; the stereochemistry is likely to be mediated by the co-ordinated isocyanide.

  Os 2 (CO) 6 µ-η 2 :η 3 -C(OH)C(CO 2 Me)CHCNHPr}] 为主要产物，[Os 2 (CO) 6 µ-η 2 ：η3-C(OH)CHC(CO 2 Me)CNHPr}] 为次要产物，其中两种 C-C 键的形成具有区域选择性，涉及炔烃和 CO 的偶联以及炔烃和 CNPr 的偶联。
• Synthesis of Os3(CO)10(CNR)(NCMe) and its reaction with propynoic acid
  作者：Kuang Lieh Lu、Chi Jung Su、Yen Wen Lin、Han Mou Gau、Yuh Sheng Wen

  DOI：10.1021/om00059a055

  日期：1992.11

  The nitrile derivatives Os3(CO)10(CNR)(NCMe) (2) have been prepared by the reaction of isocyanide complexes Os3(CO)11(CNR) (1) with Me3NO in the presence of CH3CN. The labile complex 2 on reaction with two-electron donor ligands L (L = CO, PPh3, PMePh2) gives Os3(CO)10(CNR)L (3). Treatment of 2 with propynoic acid (HC=CCO2H) in CH2Cl2 yields the hydrido complexes (mu-H)Os3(CO)10(mu2-OCOC=CH)(CNR) (4); however, complex 2 reacts with propynoic acid in acetonitrile to form complex 4 and the bridging aminocarbyne species Os3(CO)10(mu2-OCOC=CH)(mu2-C=NHR) (5) containing a unique bridging unidentate (mu2-eta1-oxo) carboxylate ligand. Molecular structures of Os3(CO)10(CNPr)(PPh3)(3a) and Os3(CO)10(mu2-OCOC=CH)(mu2-C=NHPr) (5a) have been determined by X-ray diffraction studies. Crystal data are as follows. 3a: P1BAR; a = 11.4611 (14), b = 11.6963 (19), c = 14.9661 (22) angstrom; a = 93.635 (12), beta = 73.633 (11), gamma = 117.325 (11)-degrees; V = 1705.0 (4) angstrom3, Z = 2; R = 4.2%, R(w) = 5.1%. 5a: P2(1)2(1)2(1); a = 9.4241 (23), b = 15.414 (4), c = 15.972 (3) angstrom; V = 2320.2 (9) angstrom3, Z = 4; R = 3.2%, R(w) = 3.5%.
• Novel Osmium N-Oxide Complexes from the Reaction of Triosmium Clusters with 1-Hydroxybenzotriazole
  作者：Kuang-Lieh Lu、Sudalaiandi Kumaresan、Yuh-Sheng Wen、Jih Ru Hwu

  DOI：10.1021/om00020a033

  日期：1994.8

  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.