{Ru(CO)H(MeCN)2(PPh3)2}PF6 | 126206-32-4

• 英文名称: {Ru(CO)H(MeCN)2(PPh3)2}PF6
• CAS: 126206-32-4
• 化学式: C₄₁H₃₇N₂OP₂Ru*F₆P
• 分子量: 881.739
• InChiKey: NEHRXVRQLFSMIC-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：

  {Ru(CO)H(MeCN)2(PPh3)2}PF6 在 C₂H₄(P(C₆H₅)2)2 作用下， 以 乙醇 为溶剂， 以89%的产率得到
  参考文献：
  名称：

  Synthesis of New Ruthenium(II) Carbonyl Hydrido, Alkenyl, and Alkynyl Complexes with Chelating Diphosphines

  摘要：

  Substitution of one or two triphenylphosphine ligands of Ru(CO)ClH(PPh(3))(3) by bidentate diphosphines Ph(2)P(CH2)(n)PPh(2) (L-L) (n = 1, dppm; n = 2, dppe; n = 3, dppp; n = 4, dppb) or 1, 1'-bis(diphenylphosphino)ferrocene (dppf) led to hydrides Ru(CO)ClH(PPh(3))(2)(L-L) or Ru(CO)ClH(PPh(3))(L-L). The hydride complexes were characterized spectroscopically and by one X-ray structure. Hydride Ru(CO)ClH(PPh(3))(dppf) crystallizes in the monoclinic space group P2(1)/n, with a 17.768(1) Angstrom, b = 25.252(2) Angstrom, c 11.213(1) Angstrom, beta = 92.83(1)degrees, Z = 4, and V = 4459.3(6) Angstrom(3). Reaction of Ru(CO)ClH(PPh(3))(3) or [Ru(CO)H(MeCN)(2)(PPh(3))(2)](PF6-)-P-+ with 2 equiv of diphosphines L-L led to [Ru(CO)H(L-L)(2)](+)A(-) (L-L = dppm, dppe, dppp) (A = Cl, PF6). Hydrides Ru(CO)ClH(PPh(3))(2)(L-L) react with 1-alkynes to give alkenyl complexes Ru(CO)Cl(CH=CHR)(PPh(3))(L-L) with a chelating diphosphine ligand. Ru(CO)ClH(PPh(3))(L-L) gave sigma-alkynyl complexes Ru(CO)Cl(C drop CR)L(L-L) directly in their reactions with 1-alkynes. The hydride with dppb as the ligand showed the highest reactivity. The preparation of hexaco ordinated alkenyl derivatives Ru(CO)Cl(CH=CHR)(PPh(3))(L-L) with a chelating diphosphine was carried out by treatment of other alkenyl derivatives with the diphosphines. Surprisingly, reaction of alkenyls Ru(CO)Cl(CH=CHR)(Me(2)Hpz)(PPh(3))(2) (R = CMe(3), p-MeC(6)H(4)) with dppf led to complexes Ru(CO)Cl(CH=CHR)(Me(2)Hpz)(dppf) by substitution of both PPh(3) ligands instead of the dimethylpyrazole. Ruthenium alkenyls Ru(CO)Cl(CH=CHR)L(dppf) (L = Me(2)Hpz, PPh(3)) react cleanly with 1-alkynes at room temperature to give alkynyl complexes Ru(CO)Cl(C drop CR)L(dppf) in good yield. This reaction was applied to the synthesis of a bimetallic complex Ru(CO)Cl(PPh(3))(dppf)(C drop C-p-C6H4C drop C)Ru(CO)Cl(PPh)(dppf) as a mixture of meso and dl diastereomers.

  DOI：

  10.1021/om00021a037
• 作为产物：
  描述：

  {ruthenium(II)(CO)(CHCHC6H5)(MeCN)2(PPh3)2}{PF6} 在 乙醇 作用下， 以 乙醇 为溶剂， 以62%的产率得到{Ru(CO)H(MeCN)2(PPh3)2}PF6
  参考文献：
  名称：

  Phenylacetylene dimerization promoted by ruthenium(II) complexes

  摘要：

  The complex Ru(CO)(CH = CHPh)Cl(C5,H5N)(PPh3)2 and related alkenyl complexes react in methanol or ethanol to give (E,E)-1,4-diphenylbuta-1,3-diene and the ruthenium(II) hydride Ru(CO)H(Cl)(C5H5N)(PPh3)3. Further reaction of this hydride with the butadiene results in 1,2-reduction to yield (E)-1,4-diphenyl-1-butene. However, the reaction of phenylacetylene with catalytic amounts of ruthenium hydrides gave the dimer (Z)-1,4-diphenylbuten-3-yne. On the other hand, the reaction of 1,2-diphenylethenylruthenium(II) derivatives in methanol or ethanol gave trans-stilbene rather than the butadiene. Several deuteriation experiments were performed in order to elucidate the mechanism of formation of (E, E)-1,4-diphenylbuta-1,3-diene and ruthenium hydride from the corresponding alkenyl complexes.

  DOI：

  10.1016/0022-328x(91)86337-p

文献信息

• Synthesis of RuII hydride and alkenyl amidine complexes. The crystal structure of [Ru(CO)(CH=CHCMe3){NH=C(Me)(Me2pz)}(PPh3)2]PF6
  作者：Javier López、Amelia Santos、Antonio Romero、Antonio M. Echavarren

  DOI：10.1016/0022-328x(93)80300-z

  日期：1993.1

  The reaction of the ruthenium hydrides [Ru(CO)H(R1CN)2(PPh3)2]A (A = ClO4 or PF6) (R1 = Me or CH2Ph) or the alkenyl derivatives [Ru(CO)(CH=CHR1()R2CN)2)(PPh3)2]PF6 (R1 = CMe3, Ph; R2 = Me or CH2Ph) with pyrazole or 3,5-dimethylpyrazole gives the ruthenium(II) pyrazolylamidine complexes [Ru(CO)HNH=C(R1)(het)}(PPh3)2]A or [Ru(CO)(CH=CHCR1)NH—C-(R2)(het)}(PPh3)2]A, respectively (het = pz or Me2pz).

  氢化钌[Ru（CO）H（R 1 CN）2（PPh 3）2 ] A（A = ClO 4或PF 6）（R 1 = Me或CH 2 Ph）或烯基衍生物[Ru （CO）（CH = CHR 1（）R 2 CN）2）（PPh 3）2 ] PF 6（R 1 = CMe 3，Ph; R 2 = Me或CH 2 Ph）与吡唑或3,5-二甲基吡唑得到钌（II）吡唑基咪唑配合物[Ru（CO）H NH = C（R 1）（het）}（PPh 3）2 ] A或[Ru（CO）（CH = CHCR 1）NH-C-（R 2）（het）}（PPh 3）2 ] A（het = pz或Me 2 pz）。通过NOEDIFF实验和[Ru（CO）（CH = CHCMe 3）NH = C（Me）（Me 2 pz）}（PPh 3）2的X射线结构测定，确定了所得配合物的立体化学。] PF 6。
• Reactions of cationic hydrido complexes [Ru(CO)H(MeCN)2(PPh3)2]A (A  ClO4, PF6) with alkynes. The crystal structure of [Ru(CO) (MeOOCCCHCOOMe) (MeCN)2(PPh3)2]ClO4
  作者：Javier López、Antonio Romero、Amelia Santos、Angel Vegas、Antonio M. Echavarren、Pedro Noheda

  DOI：10.1016/0022-328x(89)85051-x

  日期：1989.9

  Reactions of [Ru(CO)H(MeCN)2(PPh3)2]A with mono- and di-substituted acetylenes give the alkenyl derivatives [Ru(CO)(RCCHR′)(MeCN)2(PPh3)2]A (A  ClO4, R  H; R′  C3H7, CMe3, Ph, COOMe; R  R′  COOMe; A  PF6, R  R′  Ph) resulting from a cis-insertion of the alkyne into the RuH bond. The reaction of the perchlorate complex with diphenylacetylene yields alkenyl chlororuthenium derivatives resulting

  [Ru（CO）H（MeCN）2（PPh 3）2 ] A与单或二取代乙炔的反应，得到烯基衍生物[Ru（CO）（RCCHR'）（MeCN）2（PPh 3）2 ] A（A = ClO 4，R H； R'C 3 H 7，CMe 3，Ph，COOMe； R R R'COOMe； A PF 6，R R'R Ph）由炔顺式插入RuH键。高氯酸根络合物与二苯乙炔的反应产生烯基氯钌衍生物，这是由于高氯酸根阴离子意外还原为氯离子所致。
• The Effect of N-Donor Ligands on the Reaction of Ruthenium Hydrides with 1-Alkynes
  作者：Amelia Santos、Javier López、Amalia Galán、Juan J. González、Pilar Tinoco、Antonio M. Echavarren

  DOI：10.1021/om970054q

  日期：1997.7.1

  Neutral ruthenium hydrides Ru(CO)ClH(L)(PPh3)(2) bearing one N-donor ligand react with 1-alkynes at 23 degrees C to yield neutral alkenyl complexes Ru(CO)Cl(CH=CHR)(L)(PPh3)(2). Under similar conditions, cationic hydride complexes [Ru(CO)H(L)(2)(PPh3)(2)]PF6 with pyridine-type N-donor ligands yield alkynyl complexes [Ru(CO)(CH=CHR)(L)(2)(PPh3)(2)]PF6 as a result of the reaction of the intermediate labile alkenyl with a second molecule of alkyne, Under more forcing conditions, 1-alkynyl complexes could also be prepared from the neutral ruthenium hydrides. Cationic ruthenium hydrides with bidentate N-donor ligands are unreactive toward 1-alkynes, Neutral alkenyl complexes Ru(CO)Cl(CH=CHR)(L)(PPh3)(2) (R = p-MeC6H4, CMe3; L = pyridine, isoquinoline) reacted smoothly with 1-alkynes to afford the corresponding sigma-alkynyl ruthenium derivatives Ru(CO)Cl(C=CR)(L)(PPh3)(2).
• Monomeric and dimeric ruthenium-TCNQ complexes containing phosphine ligands (TCNQ = 7,7,8,8-tetracyanoquinodimethane)
  作者：L. Ballester、M.C. Barral、R. Jiménez-Aparicio、B. Olombrada

  DOI：10.1016/0277-5387(95)00275-w

  日期：1996.1

  Treatment of [Ru(CO)(2)(PPh(3))(2)(THF)(2)] (BF4)(2) with LiTCNQ (TCNQ = 7,7,8,8-tetracyanoquinodimethane)in dichloromethane at reflux resulted in the formation of [Ru(CO)(2)(PPh(3))(2)(TCNQ)]BF4 (1). The synthesis of the carbonylhydride compound [RuH(CO) (PPh(3))(2)(TCNQ)](2) (2) was carried out by reaction of RuHCl(CO)(PPh(3))(3) and TCNQ or from [RuH(CO) (PPh(3))(2)(CH3CN)(2)]PF6 and LiTCNQ. The preparation of compounds with diphosphines [Ru(dppe)(2)(TCNQ)](2)TCNQ(ClO4) (3) and [Ru(dppm)(3) TCNQ]ClO4 (4) is also described. In all cases substitution reactions of labile ligands occurred with formation of compounds with sigma-coordinated TCNQ. From IR, UV-vis, H-1 and P-31 NMR spectroscopy and FAB mass spectrometric determinations, monomeric and dimeric compounds are proposed.
• Ryan, Olav B.; Tilset, Mats; Parker, Vernon D., Organometallics, 1991, vol. 10, # 1, p. 298 - 304
  作者：Ryan, Olav B.、Tilset, Mats、Parker, Vernon D.

  DOI：——

  日期：——