(THF)Zr(MesNPiPr2)3Co | 1204007-60-2

• 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: (THF)Zr(MesNPiPr2)3Co
• 英文别名: (THF)Zr(MesNPiPr₂)₃Co；Zr(THF)(N(Mes)P(iPr)2)Co；Co((i)Pr2PNMes)3Zr(THF)
• CAS: 1204007-60-2
• 化学式: C₄₉H₈₃CoN₃OP₃Zr
• 分子量: 973.356
• InChiKey: AOCPIDRBULARJF-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：

  (THF)Zr(MesNPiPr2)3Co 以 四氢呋喃 、 甲苯 为溶剂， 反应 0.42h， 生成 (κ²-AcO)Zr(MesNPiPr₂)₃Co(CO)
  参考文献：
  名称：

  Zr / Co杂双金属配合物与CO 2还原相关的阴离子Zr–Oxo的合成，结构和反应活性

  摘要：

  将CO 2氧化添加到还原的Zr / Co络合物（THF）Zr（MesNP i Pr 2）3 Co（1）中，然后单电子还原导致形成异常的末端Zr-氧代阴离子[ 2] [Na（ THF）3 ]收率低。为了促进对该化合物的进一步研究，已经设计了替代的高产率合成途径。首先，用CO处理1以形成（THF）Zr（MesNP i Pr 2）3 Co（CO）（3）；然后，向3中添加H 2 O会生成Zr-氢氧化物络合物（HO）Zr（MesNP i Pr2）3 Co（CO）（4）。Li（N（SiMe 3）2）对4的质子化导致在不存在或存在下阴离子Zr–oxo物种[2] [Li（THF）3 ]或[2] [Li（12-c-4）]分别为12冠4。Li +抗衡阳离子的配位域显示出导致这两个物种之间有趣的结构差异。络合物[2] [Li（12-c-4）]中的阴离子氧代片段与亲电试剂如MeOTf和Me 3 SiOTf反应，生成（MeO）Zr（MesNP

  DOI：

  10.1021/ic302473j
• 作为产物：
  描述：

  (tetrahydrofuran)Zr(2,4,6-trimethylphenyl-NPⁱPr₂)₃CoN₂ 以 氘代甲苯 为溶剂， 生成 (THF)Zr(MesNPiPr2)3Co
  参考文献：
  名称：

  异双金属Zr / Co和Ti / Co三（膦酰胺）配合物对酮C═O键活化过程的研究

  摘要：

  还原的Zr / Co和Ti / Co络合物（THF）Zr（MesNP i Pr 2）3 CoN 2（1，Mes = 2,4,6-三甲基苯基）和（THF）Ti（XylNP i Pr 2）的反应性探索了对二芳基酮的3 CoN 2（7，Xyl = 3,5-二甲基苯基），以期获得对C═O键断裂过程的机械理解。配合物1与4,4'-二甲氧基二苯甲酮反应生成（（p -OMeC 6 H 4）2 CO）Zr（MesNP i Pr 2）3 CoN2（2），它是价互变异构体在溶液中的混合物，它们通过电子转移从Co –I转移到2 S中与Zr结合的酮上，从而在2 T中形成Zr结合的酮基。固态的2的几何形状与单线态酮加合物互变异构体2 S最一致。在移除共同结合的N-的2在真空下，复杂的2个干净覆羽到μ氧代卡宾产物（η 2 -MesNP我镨2基）Zr（MesNP我镨2）2（μ-O）Co═C（C在室温下在溶液中为6 H 4

  DOI：

  10.1021/acs.organomet.7b00445

文献信息

• Metal−Metal Multiple Bonds in Early/Late Heterobimetallics Support Unusual Trigonal Monopyramidal Geometries at both Zr and Co
  作者：Bennett P. Greenwood、Gerard T. Rowe、Chun-Hsing Chen、Bruce M. Foxman、Christine M. Thomas

  DOI：10.1021/ja909310t

  日期：2010.1.13

  Reduction of Zr/Co heterobimetallic complexes lCo(MesNP(l)Pr(2))(3)ZrCl (1) and lCo((PrNPPr2)-Pr-l-Pr-l)(3)ZrCl (2) with excess Na/Hg under N-2), followed by subsequent benzene extraction to remove coordinated Na halide salts, leads to neutral two-electron reduced, dinitrogen-bound complexes (THF)Zr(MesNP(l)Pr(2))(3)Co-N-2 (4) and Zr((PrNPPr2)-Pr-l-Pr-l)(3)Co-N-2 (5). Upon halide loss, a THF solvent Molecule coordinates to the axial site of the Zr center in 4, while this axial site remains unoccupied in 5. X-ray crystallography reveals short Co-Zr distances in 4 and 5, indicative of metal-metal multiple bonding, and an unprecedented trigonal monopyramidal geometry about the Zr center in 5. Reduction of 4 under an Ar atmosphere (in the absence of N2) results in another unusual structure type: an unoccupied axial Co coordination site and a trigonal monopyramidal Co center in (THF)Zr(MesNP(l)Pr,)(3)Co (6). X-ray crystallography reveals that, in the absence of coordinated N2, the Co-Zr bond can attain full triple bond character with a Co-Zr distance of 2.14 angstrom, the shortest M-M distance in an early/late heterobimetallic complex reported to date. To further assess the electronic structure and bonding in 4, 5, and 6, calculations were performed on these molecules using DFT and the results of these theoretical investigations will be discussed.
• Activation of CO₂ by a Heterobimetallic Zr/Co Complex
  作者：Jeremy P. Krogman、Bruce M. Foxman、Christine M. Thomas

  DOI：10.1021/ja2071847

  日期：2011.9.21

  At room temperature, the early/late heterobimetallic complex Co((i)Pr(2)PNMes)(3)Zr(THF). has been shown to oxidatively add CO2, generating (OC)Co((i)Pr(2)PNMes)(2) (mu-O)Zr((i)Pr(2)PNMes). This compound can be further reduced under varying conditions to generate either the Zr oxoanion (THF)(3)Na-O-Zr(MesNP(i)Pr(2))(3)Co(CO) or the Zr carbonate complex (THF)(4)Na-2(CO3)-Zr(MesNP(i)Pr(2))(3) Co (CO). Additionally, reactivity of the CO2-derived product has been observed with PhSiH3 to generate the Co-hydride/Zr-siloxide product (OC)(H)Co((i)Pr(2)PNMes)(3)ZrOSiH2Ph.