cis-[Ru(1,2-bis(dimethylphosphino)ethane)2(CO3)] | 135832-20-1

• 分子结构分类: 有机化合物
• 英文名称: cis-[Ru(1,2-bis(dimethylphosphino)ethane)2(CO3)]
• CAS: 135832-20-1
• 化学式: C₁₃H₃₂O₃P₄Ru
• 分子量: 461.36
• InChiKey: PDQVTYIGJGCLJZ-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  5.0
• 重原子数：
  21.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为产物：
  描述：

  在 CO₂ 作用下， 以 四氢呋喃 、 氘代苯 为溶剂， 生成 cis-[Ru(1,2-bis(dimethylphosphino)ethane)2(CO3)]
  参考文献：
  名称：

  Structure and reactions of oxametallacyclobutanes and oxametallacyclobutenes of ruthenium

  摘要：

  Structure and reactivity studies are reported with the ruthenium metallacycles prepared as described in the previous paper. A C-C cleavage reaction by an apparent beta-Me elimination pathway at 45-degrees-C is reported for the PMe3-substituted oxametallacyclobutane complex (PMe3)4Ru(OC(Me)(Ph)CH2) (1), while the analogous DMPE-substituted metallacyclobutane (DMPE)2Ru(OC(Me)(Ph)CH2) (2) is stable at 140-degrees-C. Similarly, compound 1 undergoes insertion of CO into the metal-carbon bond, while 2 is inert toward this substrate. Addition of protic acids and electrophiles leads to rapid extrusion of alpha-methylstyrene with both metallacycles. X-ray structural analysis of the acetone dianion complex (PMe3)4Ru((CH2)2CO) (17) was performed and displays a dihedral angle of 46-degrees-C in the metallacycle. In contrast, the 4,4-dimethyl-2-butanone dianion complex (PMe3)4Ru(CH2C(CHCMe3)O) (15) contains a flat metallacycle that is bound through the CH2 group and the oxygen atom. Reactivity studies with 15 showed that, unlike compounds 1 and 2, the organic portion remained intact upon addition of protic acids. The addition of 4,4-dimethyl-2-butanone led to a second C-C cleavage reaction, forming the di-tert-butylacetylacetonate complex (PMe3)3Ru(Me)(CH(COCH2CMe3)2) (19). Reactivity studies with 17 showed reversible formation of the isolable oxatrimethylenemethane complex 18, which was isolated and structurally characterized. Addition of acetone to 17 led to formation of mesityl oxide dianion complex (PMe3)4Ru(OC(Me)CHC(Me)CH) (19); mesityl oxide is presumably formed by aldol condensation at the metal center. Reactivity studies of the oxametallacyclobutene complex (PMe3)4Ru(OC(CMe3)CH) showed formation of free ketone upon addition of protic acids and insertion into the metal-oxygen bond upon addition of CO2. The metallacycle was converted to the silyl enol ether upon addition of trimethylsilane and to the free ketone following addition of H-2.

  DOI：

  10.1021/om00055a061

文献信息

• Insertion of CO₂ into the Ru−C Bonds of <i>cis-</i> and <i>trans</i>-Ru(dmpe)₂Me₂ (dmpe = Me₂PCH₂CH₂PMe₂)
  作者：Olivia R. Allen、Scott J. Dalgarno、Leslie D. Field、Paul Jensen、Anthony C. Willis

  DOI：10.1021/om801184k

  日期：2009.4.27

  Ru(dmpe)2(O2CCH3)H (12) as the thermodynamic product. This means that the insertion of CO2 into the Ru−H bond is kinetically favored, but the thermodynamic product results from insertion into the Ru−C bond. All complexes have been characterized by multinuclear NMR spectroscopy, with IR spectroscopy and elemental analyses where complexes were thermally stable. Complexes 5, 7, 8, and 12 have also been characterized

  研究了顺式-Ru（dmpe）2 Me 2（1）和反式-Ru（dmpe）2 Me 2（2）[dmpe = 1，2-双（二甲基膦基）乙烷]与二氧化碳的反应。在300 K下向反式-Ru（dmpe）2 Me 2（2）中添加3−4 atm的CO 2导致形成预期的乙酸甲酯络合物反式-Ru（dmpe）2（OCOMe）Me（3）和双乙酸酯复合物反式-Ru（dmpe）2（OCOMe）2（5）。将300 K下的3−4 atm CO 2添加到顺式-Ru（dmpe）2 Me 2（1）导致形成预期的乙酸甲酯络合物顺式-Ru（dmpe）2（OCOMe）Me（4）和反应混合物在333 K加热时，生成双乙酸盐络合物的顺式-Ru（dmpe）2（OCOMe）2（6）。在两者中均形成碳酸盐副产物Ru（dmpe）2 CO 3（7）。反应。作为这项研究的一部分，合成了一种新的钌甲基氢化物配合物Ru（dmpe）2据报道CH 3 H（8）及其异构化性质和与CO