chloronitrosylbis(triphenylphosphine)ruthenium

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: chloronitrosylbis(triphenylphosphine)ruthenium
• 英文别名: bis(triphenylphosphine)nitrosylchlororuthenium；Chlororuthenium(1+);nitroxyl anion;triphenylphosphane
• 化学式: C₃₆H₃₀ClNOP₂Ru
• 分子量: 691.111
• InChiKey: VWGHAHFXNRCVHU-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  7.9
• 重原子数：
  42
• 可旋转键数：
  6
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  18.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  chloronitrosylbis(triphenylphosphine)ruthenium 在 zinc-copper couple 作用下， 以 氘代苯 为溶剂， 生成
  参考文献：
  名称：

  Synthesis and reactions of Ru(CH₂)Cl(NO)(PPh₃)₂, a stable terminal methylene complex and the crystal structure of Ru(CH₂PPh₃)(η²-C₂F₄)Cl(NO)(PPh₃)

  摘要：

  Treatment of RuCl(NO)(PPh3)2 with CH2N2 in diethyl ether at room temperature affords Ru(= CH2)Cl(NO)(PPh3)2 1. Complex 1 undergoes a reaction with each of the reagents HCl, [Aul2]-, HgCl(C6H4Me-p), HgCl2 and SO2 forming respectively RuMeCl2(NO)(PPh3)2 2, R activated u(CH2Aul)Cl(NO)(PPh3)2 3, Ru[CH2Hg(C6H4Me-p)]Cl2(NO)(PPh3)2 4a, Ru(CH2HgCl)Cl2(NO)(PPh3)2 4b and R activated u[CH2S(O)O]Cl(NO)(PPh3)2 5. Treatment of 1 with PhC2Ph at room temperature affords the unstable complex Ru(CH2PPh3)(eta-2-PhC2Ph)Cl(NO)(PPh3) 6. Reaction of 1 with ethylene under the same conditions gives, as a final product, Ru(eta-2-C2H4)Cl(NO)(PPh3)2 11. An NMR investigation of the production of 11 confirmed the presence of the intermediate Ru(CH2PPh3)(eta-2-C2H4)Cl(NO)(PPh3) 10, and the formation of propene as 11 was generated, suggesting a possible metallacyclopropane intermediate. In contrast, treatment of 1 with C2F4 yields Ru(CH2PPh3)(eta-2-C2F4)Cl(NO)(PPh3) 7, exclusively, the structure of which was confirmed by single-crystal X-ray diffraction. The metal geometry is that of a distorted trigonal bipyramid, with the triphenylphosphine and the ylide carbon occupying the apical sites. The osmium analogue of 7, Os(CH2PPh3)(eta-2-C2F4)Cl(NO)(PPh3) 8, is obtained from a similar reaction.

  DOI：

  10.1039/dt9910000609
• 作为产物：
  描述：

  在 三苯基膦 作用下， 以 苯 为溶剂， 生成 chloronitrosylbis(triphenylphosphine)ruthenium
  参考文献：
  名称：

  Ruthenium nitrosyl complexes with bridging sulfide and sulfur monoxide as ligands

  摘要：

  DOI：

  10.1016/0584-8539(83)80176-7

文献信息

• Carbene complexes. Part 15. The synthesis and properties of electron-rich olefin-derived mono-and oligo-carbenenitrosyl-ruthenium, -osmium, and -nickel complexes
  作者：Michael F. Lappert、Peter L. Pye

  DOI：10.1039/dt9780000837

  日期：——

  are displaced from [Ni(NO)(PPh3)2X] to give [Ni(LR)2(NO)X](X = Cl, R = Et; X = Br, R = CH2Ph). Spectro-scopic data (1H and 13C n m.r. and i.r.) of the new complexes are reported. Many of the complexes exhibit com-plicated 1H n.m.r. spectra because of the inequivalence of N–CH2Ph protons or N–CH3 groups, caused by restricted rotation [ΔG‡(rotation) >25 kcal mol–1 about M–Ccarb, bonds]. Several trends

  富含电子的烯烃[：[省略图示] R] 2（L R 2； R = Me，Et或CH 2 Ph）易于将[RuCl 3（NO）（PPh 3）2 ]还原为[RuCl（NO） （PPh 3）2 ]，然后（a）（R = Me）与过量的烯烃反应，得到对双氧和水敏感的[Ru（L ME）4（NO）] Cl（1），或（b）（R = CH 2 Ph）产生[RuCl（L CH3PH）2（NO）]（3）。配合物（1）容易被Ag +氧化，生成反式-[RuCl（L ME）4（NO）] X 2（X = [BF 4 ]或[ClO 4 ]）并与CO反应，得到反式-[Ru（CO）Cl（L ME） 4 ] Cl。相反，配合物（3）被Mel或PhCH 2 Cl氧化，生成[RuMe（Cl）I（L CH3PH） 2（NO）]（8）或[RuCl 3（L CH3PH） 2（NO）]（9 ）并与CO一起生成[Ru（CO）Cl（L CH3PH）
• The reaction of formyl fluoride with transition metal complexes
  作者：Gerald Doyle

  DOI：10.1016/s0022-328x(00)93176-0

  日期：1982.1

  Formyl fluoride reacts with metal carbonyl anions in a manner similar to acetic formic anhydride. Although formyl complexes may have been formed as unstable intermediates, no neutral formyl complexes could be isolated but rather the expected decomposition products, the metal carbonyl hydrides or ?imers, were produced. The attempted oxidative addition of formyl fluoride to various coordinately unsaturated

  甲酰氟与羰基金属阴离子以类似于乙酸酐的方式反应。尽管甲酰基络合物可能已经形成为不稳定的中间体，但无法分离出中性甲酰基络合物，而是产生了预期的分解产物，即羰基金属氢化物或辉石。尝试将甲酰氟氧化加成到各种配位不饱和金属络合物中也未导致形成甲酰基衍生物。HF加合物由与甲酰氟反应的ffrr（CO）Cl（PR 3）2或M（PPh 3）4（MPt或Pd）与Ru（NO）Cl（PPh 3）2和Rh（PPh）反应制得3）3Cl分别给出CO配合物Ru（NO）（CO）Cl（PPh 3）2和Rh（CO）Cl（PPh 3）2。
• Reactions of Thiocarbamoyl compounds with vaska complexes: mechanism and stereochemistry
  作者：W.K. Dean

  DOI：10.1016/s0022-328x(00)90628-4

  日期：1980.5

  known reactions of Vaska-type complexes with Me2NCSCl to give [trans-(Ph3P)2Ir(η2-CSNMe2)COCl]Cl and trans-(Ph3P)2Rh(η2-CSNMe2)Cl2 probably follow a similar course. (PH3P)RuNOCl reacts with (Me2NCS)2S and Me2NCSCl in the same way as (Ph3P)2IrCOCl, but reacts with (Me2NCS)2NPh to give [trans-(Ph3P)2Ru(η2-CSNMe2)NOCl]PF6. The mechanism and stereochemistry of these reactions are discussed. Reactions were

  双（甲基硫代氨基甲）硫醚，（ME 2 NCS）2 S，用（PH发生反应3 P）2个MCOCl络合物赋予离子物质[PH 3 PM（η 2 -CSNMe 2）（S 2 CNME 2）CO] X（M = Rh，Ir； X ＝ Cl，PF 6）为动力学产物。静置溶液，[PH 3 PRH（η 2 -CSNMe 2）（S 2 CNME 2）CO] C1被缓慢转化为热力学产物的PH值3 PRH（η 2 -CSNMe 2）S 2 CNME 2Cl。沃什卡型复合物与我的已知反应2 NCSCl，得到[反式- （PH 3 P）2的Ir（η 2 -CSNMe 2）氯化钴] Cl和反式- （PH 3 P）2的Rh（η 2 -CSNMe 2 Cl 2可能遵循类似的过程。（PH 3 P）RuNOCl以与（Ph 3 P）2 IrCOCl相同的方式与（Me 2 NCS）2 S和Me 2 NCSCl反应，但与（Me 2 NCS）2
• Reactions of 3-trimethylsilyl-2-(methylsulphonyloxymethyl)prop-1-ene with low-valent complexes of molybdenum, ruthenium, osmium, rhodium, iridium, palladium, and platinum. New syntheses of η⁴-trimethylenemethane complexes of ruthenium, osmium, and iridium
  作者：Michael D. Jones、Raymond D. W. Kemmitt

  DOI：10.1039/c39850000811

  日期：——

  The η4-trimethylenemethane (tmm) metal complexes [MCl(NO)(PPh3)(tmm)](M = Ru or Os), [Os(CO)2(PPh3)(tmm)], [IrX(CO)(L)(tmm)](X = Cl, L = PPh3 or AsPh3; X = Br, L = PPh3), [IrCl(PPh3)2(tmm)], and [Ir(CO)(PPh3)2(tmm)][OS(O)2Me] have been prepared in good yields by the action of Me3SiCH2C(CH2)-CH2OS(O)2Me} upon [MCl(NO)(PPh3)n](M = Ru, n= 2; M = Os, n= 3), [IrX(CO)L2], [Ir2Cl2(C8H14)4]+ 4PPh3, and [IrH(CO)(PPh3)3]

  的η 4 -trimethylenemethane（TMM）金属配合物[的MC1（NO）（PPH 3）（TMM）]（M = Ru或OS），[OS（CO）2（PPH 3）（TMM）]，[IRX（CO ）（L）（tmm）]（X = Cl，L = PPh 3或AsPh 3； X = Br，L = PPh 3），[IrCl（PPh 3）2（tmm）]和[Ir（CO）（ PPh 3）2（tmm）] [OS（O）2 Me]是通过Me 3 SiCH 2 C（CH 2）-CH 2 OS（O）2 Me}对[MCl（ NO）（PPh 3）n ]（M = Ru，n = 2；M ＝ Os，n＝ 3），[IrX（CO）L 2 ]，[Ir 2 Cl 2（C 8 H 14）4 ] + 4PPh 3和[IrH（CO）（PPh 3）3 ]。
• Synthesis and characterisation of C60 derivatives containing functionalised anthraquinone groups and an unusual fullerene-stabilised cation
  作者：Wolfgang Bidell、Richard G Compton、John C Eklund、Malcolm L.H Green、Thomas O Rebbitt、Adam H.H Stephens

  DOI：10.1016/s0022-328x(98)00436-7

  日期：1998.7

  ortho-anthraquinonedimethane dienophiles prepared in situ from 1,4-dihydroxy-2,3-bis(bromomethyl)-anthraquinone and 1,4-dimethoxy-2,3-bis(bromomethyl)anthraquinone respectively react with the fullerene C60 to give the anthraquinone derivatives: dihydroxy-anthraquinone-C60 and dimethoxy-anthraquinone-C60. The former compound with sodium butoxide and 15-crown-5 gives the bis(sodium-15-crown-5)dioxo-anthraquinone-C60

  的邻位由1,4-二羟基-2,3-双（溴甲基）原位制备-anthraquinonedimethane亲二烯体-蒽醌和1,4-二甲氧基-2,3-双（溴甲基）蒽醌分别与富勒烯C反应60，得到蒽醌衍生物：二羟基蒽醌-C 60和二甲氧基蒽醌-C 60。与丁醇钠和15-冠5的前一种化合物得到双（钠-15-冠-5）二氧杂蒽醌-C 60。所述二甲氧基蒽醌-C 60分发生反应，以[Ru（PPH 3）2（NO）CL]，以形成双加合物[ η 2 - （二甲氧基-蒽醌-C 60）]的[Ru（PPH 3）2（NO）Cl]}。已经通过循环伏安法研究了二羟基和二甲氧基蒽醌-C 60衍生物的电化学，与1,4-二羟基-2,3-二甲基蒽醌相反，化合物二羟基-蒽醌-C 60显示两个独立的一个电子在较低电位下的氧化强烈表明富勒烯稳定阳离子的一个相对罕见的例子。