(η(5)-pentamethylcyclopentadienyl)dicarbonyl(η(2)-(3-hydroxy)propine)rhenium | 179030-13-8

• 英文名称: (η(5)-pentamethylcyclopentadienyl)dicarbonyl(η(2)-(3-hydroxy)propine)rhenium
• CAS: 179030-13-8
• 化学式: C₁₅H₁₉O₃Re
• 分子量: 433.521
• InChiKey: XSZRDRLGKGSSBO-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：

  四氟硼酸-二乙醚络合物 、 (η(5)-pentamethylcyclopentadienyl)dicarbonyl(η(2)-(3-hydroxy)propine)rhenium 以 二氯甲烷 为溶剂， 以89%的产率得到
  参考文献：
  名称：

  Synthesis of η³-Propargyl Rhenium Complexes

  摘要：

  Hybride abstraction from eta(2)-alkyne rhenium complexes C(5)Me(5)(CO)(2)Re(RC=CR') (2) with Ph(3)C(+)PF(6)(-) produces eta(3)-propargyl complexes C(5)Me(5)(CO)(2)Re(eta(3)-CHR ''-C=CR)(PF6-)-P-+ (3). Successful hydride abstraction to produce eta(3)-propargyl complexes was observed only for internal acetylenes with a methyl or primary alkyl substituent. an unusual regioselectivity for hydride abstraction was observed: CH3CH2>CH3 much greater than CH(CH3)(2). Hydride abstraction from diethylacetylene complex C(5)Me(5)(CO)(2)Re(eta(2)-CH3CH2C=CCH2CH3) (2c) produced a single stereoisomer of eta(3)-propargyl complex C(5)Me(5)(CO)(2)Re(eta(3)-CH3CH-C=CCH2CH3)(PF6-)-P-+ (3c) in which it is suggested that the methyl group is located in the less crowded position anti to the Cp* group. the regio- and stereoselectivity of hydride abstraction can be explained in terms of transition stat A in which the carbon hydrogen bond being cleaved is antiperiplanar with respect to rhenium and the syn propargylic substituent comes into close contact with the Cp* ligand. Protonation of C(5)Me(5)(CO)(2)Re(eta(2)-HC=CCH2OH) (6h) with HBF4-Et(2)O gave C(5)Me(5)(CO)(2)Re(eta(3)-CH2-Me(5)(CO)(2)Re(eta(2)-HC=CCH3) (2h). Protonation of propargyl alcohol complexes provides a regiospecific synthesis of pi-propargyl complexes: protonation of C(5)Me(5)(CO)(2)Re(eta(2)-CH3CH2C=CCH2OH) (6e) gave C(5)Me(5)(CO)(2)Re(eta(3)-CH2-C=CCH2CH3)(BF4-)-B-+ (3c-BF4), while protonation of C(5)Me(5)(CO)(2)Re[eta(2)-CH3C=CCH(CH3)OH] (6d) gave C-5-Me(5)(CO)(2)Re(eta(3)-CH3CH-C=CCH3)(BF4-)-B-+ (anti-ed-BF4).

  DOI：

  10.1021/ja960375d
• 作为产物：
  描述：

  (pentamethylcyclopentadienyl)(CO)2Re(tetrahydrofuran) 、 2-丙炔-1-醇 以 四氢呋喃 为溶剂， 以66%的产率得到(η(5)-pentamethylcyclopentadienyl)dicarbonyl(η(2)-(3-hydroxy)propine)rhenium
  参考文献：
  名称：

  Synthesis of η³-Propargyl Rhenium Complexes

  摘要：

  Hybride abstraction from eta(2)-alkyne rhenium complexes C(5)Me(5)(CO)(2)Re(RC=CR') (2) with Ph(3)C(+)PF(6)(-) produces eta(3)-propargyl complexes C(5)Me(5)(CO)(2)Re(eta(3)-CHR ''-C=CR)(PF6-)-P-+ (3). Successful hydride abstraction to produce eta(3)-propargyl complexes was observed only for internal acetylenes with a methyl or primary alkyl substituent. an unusual regioselectivity for hydride abstraction was observed: CH3CH2>CH3 much greater than CH(CH3)(2). Hydride abstraction from diethylacetylene complex C(5)Me(5)(CO)(2)Re(eta(2)-CH3CH2C=CCH2CH3) (2c) produced a single stereoisomer of eta(3)-propargyl complex C(5)Me(5)(CO)(2)Re(eta(3)-CH3CH-C=CCH2CH3)(PF6-)-P-+ (3c) in which it is suggested that the methyl group is located in the less crowded position anti to the Cp* group. the regio- and stereoselectivity of hydride abstraction can be explained in terms of transition stat A in which the carbon hydrogen bond being cleaved is antiperiplanar with respect to rhenium and the syn propargylic substituent comes into close contact with the Cp* ligand. Protonation of C(5)Me(5)(CO)(2)Re(eta(2)-HC=CCH2OH) (6h) with HBF4-Et(2)O gave C(5)Me(5)(CO)(2)Re(eta(3)-CH2-Me(5)(CO)(2)Re(eta(2)-HC=CCH3) (2h). Protonation of propargyl alcohol complexes provides a regiospecific synthesis of pi-propargyl complexes: protonation of C(5)Me(5)(CO)(2)Re(eta(2)-CH3CH2C=CCH2OH) (6e) gave C(5)Me(5)(CO)(2)Re(eta(3)-CH2-C=CCH2CH3)(BF4-)-B-+ (3c-BF4), while protonation of C(5)Me(5)(CO)(2)Re[eta(2)-CH3C=CCH(CH3)OH] (6d) gave C-5-Me(5)(CO)(2)Re(eta(3)-CH3CH-C=CCH3)(BF4-)-B-+ (anti-ed-BF4).

  DOI：

  10.1021/ja960375d

文献信息

• Kinetic Addition of Nucleophiles to η³-Propargyl Rhenium Complexes Occurs at the Central Carbon to Produce Rhenacyclobutenes
  作者：Charles P. Casey、John R. Nash、Chae S. Yi、Anthony D. Selmeczy、Steven Chung、Douglas R. Powell、Randy K. Hayashi

  DOI：10.1021/ja9729847

  日期：1998.2.1

  metallacyclobutene complexes. Pyridine added to the central propargyl carbon of 3b at low temperature to produce the metastable metallacyclobutene C5Me5(CO)2ReCH2C(NC5H5)CCH3+PF6- (14b) which rearranged to the η2-allene complex C5Me5(CO)2Re[η2-H2CCC(NC5H5)CH3]+PF6- (15K) at room temperature. 4-(Dimethylamino)pyridine (DMAP) added to the central carbon of the tert-butyl-substituted η3-propargyl complex 3a below

  亲核试剂的动力学加成发生在 η3-炔丙基铼配合物的中心碳上以产生环丁烯。P(CH3)3 与 C5Me5(CO)2Re[η3-CH2C⋮CC( )3]+BF4- (3a) 反应得到金属环丁烯 C5Me5(CO)2ReCH2C(PMe3)CC( )3+ - ( 4a)，其特征在于 X 射线晶体学。丙二酸酯和乙炔亲核试剂与 C5Me5(CO)2Re[η3-CH2C⋮C ]+PF6-(3b) 反应得到金属环丁烯配合物。在低温下将吡啶加到 3b 的中心炔碳上，生成亚稳态金属环丁烯 C5Me5(CO)2ReCH2C(NC5H5)C +PF6-(14b)，重排为 η2-丙二烯配合物 C5Me5(CO)2Re[η2-H2CCC( NC5H5) ]+PF6- (15K) 在室温下。
• η3-Propargyl complexes of molybdenum, tungsten, and rhenium
  作者：E. S. Taits、P. V. Petrovskii、V. V. Krivykh

  DOI：10.1007/bf02494828

  日期：1999.9

  The reactions of the MenC6H6−nM(CO)3 (M=Cr, Mo, W;n=3, 5, 6) and C5R5M(CO)3 (M=Mn, Re; R=H, Me) complexes with propargyl alcohol in acidic media under UV irradiation were studied. Novel MenC6H6−nM(CO)2(η3-C3H3)BF4 (M=Mo, W;n=3, 5, 6) and C5R5Re(CO)2(η3-C3H3)CF3SO3 complexes with the 3ē-propargyl ligand were synthesized, and their properties compared with those of similar η3-allyl derivatives. The structure

  MenC6H6−nM(CO)3 (M=Cr, Mo, W;n=3, 5, 6) 和 C5R5M(CO)3 (M=Mn, Re; R=H, Me) 与炔丙基配合物的反应研究了在紫外线照射下酸性介质中的酒精。合成了具有 3ē-炔丙基配体的新型 MenC6H6−nM(CO)2(η3-C3H3)BF4 (M=Mo, W;n=3, 5, 6) 和 C5R5Re(CO)2(η3- )CF3SO3 配合物，以及它们的性质与类似的 η3-烯丙基衍生物的性质相比。讨论了所得化合物的结构和动力学性质。