Ru2(CO)4(μ-H)(.mu-P(t)Bu2)(μ-diphenylphosphinomethane) | 225092-99-9

• 英文名称: Ru2(CO)4(μ-H)(.mu-P(t)Bu2)(μ-diphenylphosphinomethane)
• 英文别名: [Ru2(CO)4(μ-H)(μ-P(t)Bu2)(μ-dppm)]；[Ru2(CO)4(μ-H)(μ-P(t-Bu)2)(μ-di(phenylphosphino)methane)]；Ru2(CO)4(μ-H)(μ-P(t-Bu)2)(μ-dppm)；[Ru2(CO)4(μ-H)(μ-PtBu2)(μ-dppm)]
• CAS: 225092-99-9
• 化学式: C₃₇H₄₁O₄P₃Ru₂
• 分子量: 844.791
• InChiKey: IUMMMJPBJOMYNL-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：

  三丁基膦 、 Ru2(CO)4(μ-H)(.mu-P(t)Bu2)(μ-diphenylphosphinomethane) 以 氘代氯仿 为溶剂， 以87%的产率得到Ru2(CO)3(P(n)Bu3)(μ-H)(.mu-P(t)Bu2)(μ-diphenylphosphinomethane)
  参考文献：
  名称：

  Boettcher, Hans-Christian; Graf, Marion; Merzweiler, Kurt, Zeitschrift fur Anorganische und Allgemeine Chemie, 2000, vol. 626, # 6, p. 1335 - 1340

  摘要：

  DOI：
• 作为产物：
  描述：

  [Ru2(CO)4(μ-H)(μ-P(t-Bu)2)(μ-di(phenylphosphino)methane)(trans-μ-η2-ONNO)] 以 二氯甲烷 为溶剂， 以0%的产率得到Ru2(CO)4(μ-H)(.mu-P(t)Bu2)(μ-diphenylphosphinomethane)
  参考文献：
  名称：

  Reductive Dimerization of Nitric Oxide to trans-Hyponitrite in the Coordination Sphere of a Dinuclear Ruthenium Complex

  摘要：

  During the reaction of the coordinatively unsaturated compound [Ru-2(CO)(4)(mu-H)(mu-PBu2t)(mu-dppm)] (1; dppm = Ph2PCH2PPh2) with nitric oxide, the latter dimerizes and yields the unusual trans-hyponitrite complex [Ru-2(CO)(4)(mu-H)(mu-PBu2t)(mu-dppm)(mu-eta(2)-ONNO)] (2). The molecular structure of 2 has been determined by X-ray diffraction and is discussed together with the results of DFT calculations. The compound stands out by having only one of the two hyponitrite NO units bonded to Ru. The second one is not connected to Ru but in the solid state exhibits a weak intramolecular bond to the carbon atom of a neighboring carbonyl group.

  DOI：

  10.1021/om030618s

文献信息

• Koordinativ ungesättigte Dirutheniumkomplexe: Synthese und Kristallstrukturen von [Ru2(CO)4(μ-H)(μ-S)(μ-PtBu2)(μ-Ph2PCH2PPh2)] und [Ru2(CO)4(μ-X)(μ-PtBu2)(μ-Ph2PCH2PPh2)] (X = Cl, S2CH)
  作者：Hans-Christian Böttcher、Marion Graf、Kurt Merzweiler、Christoph Wagner

  DOI：10.1002/(sici)1521-3749(200002)626:2<597::aid-zaac597>3.0.co;2-b

  日期：2000.2

  Ru2(μ-H) bridge the dithioformato complex [Ru2(CO)4(μ-S2CH)(μ-PtBu2)(μ-dppm)] (3). Furthermore, 1 reacts with [NO][BF4] to the complex salt [Ru2(CO)4(μ-NO)(μ-H)(μ-PtBu2)(μ-dppm)][BF4] (4), and reaction of 1 with CCl4 or CHCl3 affords spontaneously [Ru2(CO)4(μ-Cl)(μ-PtBu2)(μ-dppm)] (5) in nearly quantitative yield. The molecular structures of 2, 3 and 5 were confirmed by crystal structure analyses.

  [Ru2(CO)4(μ-H)(μ-PtBu2)(μ-dppm)] (1) 在 Benzol mit elementarem Schwefel zum Additionsprodukt [Ru2(CO)4(μ-H)(μ-S)( μ-PtBu2)(μ-dppm)] (2) (dppm = Ph2PCH2PPh2)。2 wird auch durch Reaktion von 1 mit Ethyllensulfid erhalten。Die Reaktion von 1 mit Schwefelkohlenstoff verlauft unter Einschub des CS2 in die Ru2(μ-H)-Brucke, indem der Dithioformiatokomplex [Ru2(CO)4(μ-S2CH)(μ-PtBu2)(μ-dppm)] (3) gebildet wird。Weiterhin
• Coordinatively unsaturated complexes [M2(CO)4(μ-H)(μ-PtBu2)(μ-Ph2PCH2PPh2)] (MFe, Ru): synthesis and crystal structures of [Fe2(CO)4(μ-H)(μ-SO)(μ-PtBu2)(μ-Ph2PCH2PPh2)] and [Ru2(CO)4(μ-H)(μ-SO2)(μ-PtBu2)(μ-Ph2PCH2PPh2)]
  作者：Hans-Christian Böttcher、Marion Graf、Kurt Merzweiler、Christoph Wagner

  DOI：10.1016/s0020-1693(02)01566-9

  日期：2003.7

  [Ru2(CO)4(μ-H)(μ-S)(μ-PtBu2)(μ-dppm)] (2b) by means of 3-chloroperoxybenzoic acid or H2O2 as oxidizing reagent. As the primary oxidation products of 2a or 2b the sulfur monoxide complexes [M2(CO)4(μ-H)(μ-SO)(μ-PtBu2)(μ-dppm)] (MFe, 4a; MRu, 4b) are obtained by using 3-phenyl-2-(phenylsulfonyl)-oxaziridine as oxidizing reagent. The molecular structures of 4a and 5b were confirmed by crystal structure analyses.

  [Fe 2（CO）4（μ-H）（μ- Pt Bu 2）（μ-DPPM）]（1a）与元素硫反应生成[Fe 2（CO）4（μ-H）（μ- S）（μ- Pt Bu 2）（μ-DPPM）]（2a）（DPPM = Ph 2 PCH 2 PPh 2）。1a与CCl 4或CHCl 3的反应以几乎定量的产率自发提供[Fe 2（CO）4（μ-Cl）（μ- Pt Bu 2）（μ-DPPM）]（3a）。[Ru 2（CO）4（μ-H）（μ-P吨卜2）（μ-DPPM）]（1B）反应与SO 2在THF中在正常条件下，以的[Ru 2（CO）4（μ-H）（μ-SO 2）（μ- Pt Bu 2）（μ-DPPM）]（5b）。5b也是通过[Ru 2（CO）4（μ-H）（μ-S）（μ- Pt Bu 2）（μ-DPPM）]（2b）中的硫键配体氧化而形成的氯过氧苯甲酸或H 2 O 2作为氧化剂。作为2a或2b一氧化硫配合物[M 2（CO）4（μ-H）（μ-SO）（μ-
• Protonation of metal–metal bonds: X-ray crystal structures of the complex salts [Ru2(CO)4(μ-H)(μ-Cl)(μ-PtBu2)(μ-Ph2PCH2PPh2)][BF4] and [M2(CO)4(μ-H)2(μ-PtBu2)(μ-Ph2PCH2PPh2)][BF4] (M=Fe, Ru)
  作者：Hans-Christian Böttcher、Marion Graf、Kurt Merzweiler、Christoph Wagner

  DOI：10.1016/s0022-328x(01)00777-x

  日期：2001.5

  unsaturated species [M2(CO)4(μ-H)(μ-PtBu2)(μ-dppm)] (MM) (M=Fe, 1; M=Ru, 2; dppm=Ph2PCH2PPh2) in diethylether results in rapid protonation of the dimetal vector to give the corresponding complex salts [M2(CO)4(μ-H)2(μ-PtBu2)(μ-dppm)][BF4] (1a and 2a) in nearly quantitative yield. In the same manner [Ru2(CO)4(μ-Cl)(μ-PtBu2)(μ-dppm)] (3) is protonated to yield [Ru2(CO)4(μ-H)(μ-Cl)(μ-PtBu2)(μ-dppm)][BF4]

  四氟硼酸的除配位不饱和物种[M 2（CO）4（μ-H）（μ-P吨卜2）（μ-DPPM）]（中号中号）（M =铁，1 ; M =孺，2 ; DPPM = Ph 2 PCH 2 PPh 2）在二乙醚中导致双金属载体快速质子化，得到相应的复合盐[M 2（CO）4（μ-H）2（μ- Pt Bu 2）（ μ-DPPM）] [BF 4 ]（1a和2a）接近定量的产量。以相同的方式将[Ru 2（CO）4（μ-Cl）（μ- Pt Bu 2）（μ-DPPM）]（3）质子化以产生[Ru 2（CO）4（μ-H）（ μ-Cl）（μ- Pt Bu 2）（μ-DPPM）] [BF 4 ]（3a）。为了显示这些反应1a，2a，3a和[Ru 2（CO）4（μ-H）（μ-NO）（μ- Pt Bu 2）（μ-DPPM）]的酸碱特性] [高炉4 ]（4a）由基1,8-二氮杂双环[5.4.0]十一碳-7-烯DBU去质子化以再生1，2，3和新的复杂的[Ru
• Synthese und Kristallstruktur von [Ru2(CO)4(μ-H)(μ-NO)(μ-PtBu2)(μ-PPh2CH2PPh2)]BF4
  作者：Hans-Christian Böttcher、Tobias Mayer

  DOI：10.1002/zaac.201100226

  日期：2011.10

  unambiguously the formation of complexes 3 and 4. A clean preparation of complex 2 as the sole product in form of its tetrafluoridoborate salt is only possible by reaction of 4 with tetrafluoridoboric acid in diethyl ether solution. The X-ray crystal structure of [2]BF4 is reported confirming the molecular structure of the complex 2. Using the originally described preparation route for 2 afforded in each

  重新审视了配位不饱和络合物 [Ru2(CO)4(μ-H)(μ-PtBu2)(μ-dppm)] (1, dppm = Ph2PCH2PPh2)] 与亚硝基离子的反应。即使通过改变反应条件，反应在每种情况下也不是唯一的加成产物 [Ru2(CO)4(μ-NO)(μ-H)(μ-PtBu2)(μ-dppm)]+ (2)正如我们在之前的一篇论文中所报道的那样。取而代之的是含有复合物 [Ru2(CO)4(μ-H)2(μ-PtBu2)(μ-dppm)]+ (3)、[Ru2(CO)4(μ-NO)( μ-PtBu2)(μ-dppm)] (4)，除了最初描述的复合物 2 之外，还获得了。描述了一种新的合成方法，通过 1 与亚硝基化试剂二氮杂（N-甲基-N-亚硝基-对甲苯磺酰胺）反应，得到化合物 4 作为唯一产物。发现配合物 2 可以充当强到足以使起始配合物 1 质子化的酸。因此，可以解释标题反应中组分混合物的形成。等摩尔量的
• Koordinativ ungesättigte Dirutheniumkomplexe: Synthese und Kristallstrukturen von [Ru2(CO)n(μ-H)(μ-PtBu2)(μ-Ph2PCH2PPh2)] (n = 4; 5) und [Ru2(CO)4(μ-CH2)(μ-H)(μ-PtBu2)(μ-Ph2PCH2PPh2)]
  作者：Hans-Christian Böttcher、Clemens Bruhn、Kurt Merzweiler

  DOI：10.1002/(sici)1521-3749(199904)625:4<586::aid-zaac586>3.0.co;2-b

  日期：1999.4

  The reaction of [Ru-2(mu-Co)(CO)(5)(mu-H)(mu (PBu2)-Bu-t)((Bu2PH)-Bu-t)] (2) with dppm yields the dinuclear species [Ru-2(mu-CO)(CO)(4)(mu-H)(mu-(PBu2)-Bu-t) (mu-dppm)] (3) (dppm = Ph2PCH2PPh2). Under thermal or photolytic conditions 3 loses very easily one carbonyl ligand and affords the corresponding electronically and coordinatively unsaturated complex [Ru-2(CO)(4)(mu-H)(mu-(PBu2)-Bu-t)(mu-dppm)] (4). 4 is also obtainable by an one-pot synthesis from [Ru-3(O)(12)], an excess of (Bu2PH)-Bu-t and stoichiometric amounts of dppm via the formation of [Ru-2(CO)(4)(mu-H)(mu-(PBu2)-Bu-t) ((Bu2PH)-Bu-t)(2)] (1) 4 exhibits a Ru-Ru double bond which could be confirmed by addition of methylene to the dimetallacyclopropane [Ru-2(CO)(4)(mu-CH2)(mu-H)(mu-(PBu2)-Bu-t)(mu-dppm)] (5). The molecular structures of 3, 4 and 5 were determined by X-ray crystal structure analyses.