[Os(C6H4C(O)CH3)(η2-H2)(H2O)(triisopropylphosphine)2]tetrafluoroborate | 441071-60-9

• 英文名称: [Os(C6H4C(O)CH3)(η2-H2)(H2O)(triisopropylphosphine)2]tetrafluoroborate
• 英文别名: [Os(C6H4C(O)CH3)(η2-H2)(H2O)(P(i)Pr3)2]BF4；[Os(C6H4C(O)CH3)(η2-H2)(H2O)(P(i-Pr)3)2]BF4
• CAS: 441071-60-9
• 化学式: BF₄*C₂₆H₅₃O₂OsP₂
• 分子量: 736.658
• InChiKey: SMKNJYKFBMHPRI-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：

  [Os(C6H4C(O)CH3)(η2-H2)(H2O)(triisopropylphosphine)2]tetrafluoroborate 、 丙酮肟 以 二氯甲烷 为溶剂， 以86%的产率得到[Os(C6H4C(O)CH3)(η2-H2)(N(OH)=C(CH3)2)(P(i)Pr3)2]BF4
  参考文献：
  名称：

  Reactions of an Osmium-Elongated Dihydrogen Complex with Terminal Alkynes:  Formation of Novel Bifunctional Compounds with Amphoteric Nature

  摘要：

  The trihydride complex OsH3{C6H4C(O)CH3}((PPr3)-Pr-i)(2) (1) reacts with (HBF4H2O)-H-. to give the elongated dihydrogen derivative [Os{C6H4C(O)CH3](eta(2)-H-2)(H2O)((PPr3)-Pr-i)(2)]BF4 (2), with a separation between the hydrogen atoms of the elongated dihydrogen of 1.35 Angstrom. The addition of acetone oxime to dichloromethane solutions of 2 produces the substitution of the water ligand by the oxime and the formation of Os{C6H4C(O)CH3}(eta(2)-H-2){N(OH)=C(CH3)(2)}((PPr3)-Pr-i)(2)]BF4 (3), which shows a hydrogen -hydrogen distance of 1.34 1. Complex 3 reacts with phenylacetylene, cyclohexylacetylene, and tert-butylacetylene to give acetophenone and the oximate-carbyne derivatives [OsH{K-N,K-O[ON=C(CH3)(2)]}(equivalent toCCH(2)R)((PPr3)-Pr-i)(2)] BF4 (R =Ph (4), Cy (5), Bu-t (6)). The structure of 4 has been determined by X-ray diffraction analysis. The distribution of ligands around the osmium atom can be described as a distorted trigonal bipyramid with apical phosphines and inequivalent angles within the Y-shaped equatorial plane. Complexes 4-6 have amphoteric nature, reacting with both KOH and HBF4(.)Et(2)O, The reactions with KOH afford the vinylidene derivatives OsH{K-N,K-O[ON=C(CH3)(2)]}(=C=CHR)((PPr3)-Pr-i)(2) (R = Ph (7), Cy (8), tBu (9)), whereas the reactions with (HBF4Et2O)-Et-. give the fluoro-oxime compounds [6sH[F --- HO =C(CH3)(2)]}(equivalent toCCH(2)R)((PPr3)-Pr-i)(2)]BF4 (R = Ph (10), Cy (11), tBu (12)). The structures of 7 and 11 have been determined by X-ray diffraction analysis. The distribution of ligands around the osmium atom of 7 is like that of 4, whereas the geometry around the metallic center of 11 can be rationalized as a distorted octahedron with the phosphine ligands in trans positions. Complexes 10, 11, and 12 contain a strong intramolecular F- - -H hydrogen bond between the fluorine and the OH-hydrogen atom of the oxime in the solid state and in dichloromethane solution (J(H-F) = 67.5 (10), 68.1 (11), and 68.7 (12) Hz). The formation of 4-12 is also discussed, on the basis of deuterium label experiments.

  DOI：

  10.1021/om0200656
• 作为产物：
  描述：

  tetrafluoro boric acid 、 OsH3(C6H4C(O)CH3)(P(i)Pr3)2 以 甲醇 、 乙醚 为溶剂， 以89%的产率得到[Os(C6H4C(O)CH3)(η2-H2)(H2O)(triisopropylphosphine)2]tetrafluoroborate
  参考文献：
  名称：

  Reactions of an Osmium-Elongated Dihydrogen Complex with Terminal Alkynes:  Formation of Novel Bifunctional Compounds with Amphoteric Nature

  摘要：

  The trihydride complex OsH3{C6H4C(O)CH3}((PPr3)-Pr-i)(2) (1) reacts with (HBF4H2O)-H-. to give the elongated dihydrogen derivative [Os{C6H4C(O)CH3](eta(2)-H-2)(H2O)((PPr3)-Pr-i)(2)]BF4 (2), with a separation between the hydrogen atoms of the elongated dihydrogen of 1.35 Angstrom. The addition of acetone oxime to dichloromethane solutions of 2 produces the substitution of the water ligand by the oxime and the formation of Os{C6H4C(O)CH3}(eta(2)-H-2){N(OH)=C(CH3)(2)}((PPr3)-Pr-i)(2)]BF4 (3), which shows a hydrogen -hydrogen distance of 1.34 1. Complex 3 reacts with phenylacetylene, cyclohexylacetylene, and tert-butylacetylene to give acetophenone and the oximate-carbyne derivatives [OsH{K-N,K-O[ON=C(CH3)(2)]}(equivalent toCCH(2)R)((PPr3)-Pr-i)(2)] BF4 (R =Ph (4), Cy (5), Bu-t (6)). The structure of 4 has been determined by X-ray diffraction analysis. The distribution of ligands around the osmium atom can be described as a distorted trigonal bipyramid with apical phosphines and inequivalent angles within the Y-shaped equatorial plane. Complexes 4-6 have amphoteric nature, reacting with both KOH and HBF4(.)Et(2)O, The reactions with KOH afford the vinylidene derivatives OsH{K-N,K-O[ON=C(CH3)(2)]}(=C=CHR)((PPr3)-Pr-i)(2) (R = Ph (7), Cy (8), tBu (9)), whereas the reactions with (HBF4Et2O)-Et-. give the fluoro-oxime compounds [6sH[F --- HO =C(CH3)(2)]}(equivalent toCCH(2)R)((PPr3)-Pr-i)(2)]BF4 (R = Ph (10), Cy (11), tBu (12)). The structures of 7 and 11 have been determined by X-ray diffraction analysis. The distribution of ligands around the osmium atom of 7 is like that of 4, whereas the geometry around the metallic center of 11 can be rationalized as a distorted octahedron with the phosphine ligands in trans positions. Complexes 10, 11, and 12 contain a strong intramolecular F- - -H hydrogen bond between the fluorine and the OH-hydrogen atom of the oxime in the solid state and in dichloromethane solution (J(H-F) = 67.5 (10), 68.1 (11), and 68.7 (12) Hz). The formation of 4-12 is also discussed, on the basis of deuterium label experiments.

  DOI：

  10.1021/om0200656

文献信息

• Hydride-Alkenylcarbyne to Alkenylcarbene Transformation in Bisphosphine-Osmium Complexes
  作者：Tamara Bolaño、Ricardo Castarlenas、Miguel A. Esteruelas、F. Javier Modrego、Enrique Oñate

  DOI：10.1021/ja053186g

  日期：2005.8.1

  [Os(=CHCH=CR2)(CH3CN)3(PiPr3)2][BF4](2) (R = Ph (7), Me (8)) by means of a concerted 1,2-hydrogen shift from the osmium to the carbyne carbon atom. Treatment of 2-propanol solutions of 5 with NaCl affords OsHCl2((triple bond)CCH=CPh2)(PiPr3)2 (10), which reacts with AgBF(4) and acetonitrile to give [OsHCl((triple bond)CCH=CPh2)(CH3CN)(PiPr3)2]BF(4) (11). In this solvent complex 11 is converted to [OsCl(=CHCH=CPh2

  拉长的二氢络合物 [分子式：见正文](1) 与 1,1-diphenyl-2-propyn-1-ol 和 2-methyl-3-butyn-2-ol 反应生成氢化物-羟基亚乙烯基-pi-炔醇衍生物 [OsH=C=CHC(OH)R2}eta2-HC(triple bond)CC(OH)R2}(PiPr3)2]BF4 (R = Ph (2), Me (3))，其中 pi -炔醇作为四电子供体配体。用 HBF(4) 和配位溶剂处理 2 和 3 产生双阳离子氢化物-烯基碳炔化合物 [OsH((三键)CCH=CR2)S2(PiPr3)2][BF4]2 (R = Ph, S = H (2)O (4), CH(3)CN (5); R = Me, S = CH(3)CN (6))，它们在乙腈中演变成链烯基卡宾配合物 [Os(=CHCH=CR2)( CH3CN)3(PiPr3)2][BF4](2) (R
• Reactions of Elongated Dihydrogen-Osmium Complexes Containing Orthometalated Ketones with Alkynes:  Hydride-Vinylidene-π-Alkyne versus Hydride-Osmacyclopropene
  作者：Pilar Barrio、Miguel A. Esteruelas、Enrique Oñate

  DOI：10.1021/om021043m

  日期：2003.6.1

  The trihydride complex OsH3C6F4C(6)CH3}(PiPr(3))(2) (1) reacts with HBF4.H2O to give the elongated dihydrogen derivative [OsC6F4C(O)CH3}(eta(2)-H-2)(H2O)((PPr3)-Pr-i)(2)]-BF4 (2), with a separation between the hydrogen atoms of the elongated dihydrogen of about 1.3 Angstrom. Under one atmosphere of acetylene, complex 2 and the related [OsC6H4C(O)CH3}(eta(2)-H-2)(H2O)((PPr3)-Pr-i)(2)]BF4 (3) afford the hydride-vinylidene-pi-alkyne derivative [OsH(=C=CH2) (eta(2)-HCdropCH)((PPr3)-Pr-i)(2)]BF4 (4), with the alkyne acting as a four-electron donor ligand. Complex 4 reacts with methylmagnesium chloride and acetone oxime. The first reaction gives the allyl derivative OsH(eta(3)-C3H5)(=C=CH2)(PiPr3)2 (5), whereas the second one affords the oximate-carbyne [OsHkappa-N,kappa-O[ON=C(CH3)(2)]}(dropCCH(3)-((PPr3)-Pr-i)(2)]BF4 (6). Similarly to acetylene, cyclohexyl-acetylene reacts with 2 and 3 to give [OsH(=C=CHCy)-(eta(2)-HCdropCCy)((PPr3)-Pr-i)(2)]BF4 (7), which in solution at room temperature decomposes to a mixture of unidentified products. Complexes 2 and 3 also react with phenylacetylene. The reactions lead to complex mixtures of products containing [OsH(=C=CHPh)(eta(2)-HCdropCPh)- ((PPr3)-Pr-i)(2)]BF4 (8) and [OsHC6X4C(O)CH3}C(Ph)CH2}-((PPr3)-Pr-i)(2)]BF4 (X = F (9), H (11)), as main components. In solution at room temperature, complex 8 evolves into the diphenylbutadiene derivative [OsH(eta(4)-C4H4Ph2)[eta(2)-CH2=C(CH3)]((PPr2)-Pr-i}((PPr2Pr)-Pr-i-Pr-n)]BF4 (10)- Complex 11 reacts with acetophenone to afford [OsHC6H4C(O)-CH3}(2)((PPr3)-Pr-i)(2)]BF4 (12). The X-ray structures of 4, 9, and 10 are also reported.