[PhP(CH2SiMe2NSiMe2CH2)2PPh]NbCl | 477332-53-9

• 英文名称: [PhP(CH2SiMe2NSiMe2CH2)2PPh]NbCl
• 英文别名: [P2N2]NbCl
• CAS: 477332-53-9
• 化学式: C₂₄H₄₂ClN₂NbP₂Si₄
• 分子量: 661.26
• InChiKey: GCVKJFVCCVAFLL-ZOOHPUMISA-M

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：

  [PhP(CH2SiMe2NSiMe2CH2)2PPh]NbCl 在 KC₈ 作用下， 以 四氢呋喃 为溶剂， 生成 ([PhP(CH2SiMe2NSiMe2CH2)2PPh]Nb)2
  参考文献：
  名称：

  Phosphorus Phenyl-Group Activation by Reduced Zirconium and Niobium Complexes Stabilized by the [P₂N₂] Macrocycle

  摘要：

  Reduction of [P2N2]ZrCl2 (where [P2N2] = PhP(CH2SiMe2NSiMe2CH2)2PPh) with KC8 under argon generates the phosphorus phenyl bridged bimetallic complex where the bridging phenyl groups are formally reduced to bis(allyl) dianions. Similar reduction of [P2N2]NbCl caused the one-electron reduction of the phosphorus phenyl group to generate a cyclohexadienyl moiety via a C-C bond formation between the ipso carbons of the two phenyl groups.

  DOI：

  10.1021/ja012100q
• 作为产物：
  描述：

  (PhP(CH2CSiMe2NSiMe2CH2)2PPh)NbCl(THF) 以 甲苯 为溶剂， 生成 [PhP(CH2SiMe2NSiMe2CH2)2PPh]NbCl
  参考文献：
  名称：

  铌（III）的大环配合物：包含[P 2 N 2 ]系统的单核和双核物质的合成，结构和磁行为

  摘要：

  两个混合的供体大环配体R [P 2 N 2 ]（其中R [P 2 N 2 ] = RP（CH 2 SiMe 2 NSiMe 2 CH 2）2 PR，R =环己基（Cy）或苯基（ Ph））与铌（III）一起出现。二硫代前体R [P 2 N 2 ] Li 2（S）（R = Cy，S = THF; R = Ph，S = 1,4-二恶烷）与NbCl 3（DME）（DME = 1， 2-二甲氧基乙烷）生成络合物R [P 2 N 2] NbCl（R = Cy，1 ; R = Ph，2）。对于R = Cy，单晶X射线衍射研究和可变温度磁化率测量表明，1为固态单核；1为单核。但是，类似的可变温度磁数据表明，由于观察到反铁磁交换，因此2在固态时是双核的。在溶液中，2显然是单体，类似于1。这些单核复合物之间的加合物形成也很明显。的反应2与中性供体和配位溶剂产生单核衍生物博士[P 2 Ñ 2] NbCl（L）（L

  DOI：

  10.1021/om010356z

文献信息

• Cyclohexadienyl Niobium Complexes and Arene Hydrogenation Catalysis
  作者：Michael D. Fryzuk、Christopher M. Kozak、Michael R. Bowdridge、Brian O. Patrick

  DOI：10.1021/om020395q

  日期：2002.11.1

  R[P2N2]NbCH2SiMe3 (where R[P2N2] = RP(CH2SiMe2NSiMe2CH2)2PR; R = cyclohexyl, Cy, or phenyl, Ph) in benzene or toluene causes hydride addition to the aromatic solvent resulting in the formation of the π-bonded complexes R[P2N2]Nb(η5-C6H7) (R = Cy, 1; R = Ph, 2) and R[P2N2]Nb(η5-C7H9) (R = Cy, 3; R = Ph, 4) in benzene and toluene, respectively. Performing the hydrogenation at a higher pressure of 29 atm at room temperature

  的氢解- [R [P 2 Ñ 2 ] NBCH 2森达3（其中，[R [P 2 Ñ 2 ] = RP（CH 2森达2 NSiMe 2 CH 2）2 PR; R =环己基中，Cy，或苯基中，Ph）的苯或甲苯使氢化物除了导致π键合的复合物的形成的芳族溶剂- [R [P 2 ñ 2 ]的Nb（η 5 -C 6 ħ 7）（R = CY，1 ; R = PH，2）和[R[P 2 Ñ 2 ]的Nb（η 5 -C 7 ħ 9）（R = CY，3 ; R = PH，4）在分别苯和甲苯。如在NMR光谱法和GC-MS分析中所确定的，在室温下于29atm的高压下进行氢化会导致苯催化氢化成环己烷。也可以进行甲苯加氢成甲基环己烷，但是周转频率相当低。对来自高压氢化的固体残余物的检查表明形成了π-键合的配合物1和2。H 2的添加量为29 atm 但是，这些环己二烯基衍生物在苯或甲苯中的生成没有氢化产物，表明这些物质没有催化活性。
• Nitride Formation by Thermolysis of a Kinetically Stable Niobium Dinitrogen Complex
  作者：Michael D. Fryzuk、Christopher M. Kozak、Michael R. Bowdridge、Brian O. Patrick、Steven J. Rettig

  DOI：10.1021/ja025997f

  日期：2002.7.1

  on the model complex [(PH(3))(2)(NH(2))(2)Nb](2)(mu-N(2)) was performed. Thermolysis of ([P(2)N(2)]Nb)(2)(mu-N(2)) in toluene generates the paramagnetic bridging nitride species where one N atom of the dinitrogen ligand inserts into the macrocycle backbone to form [P(2)N(2)]Nb(mu-N)Nb[PN(3)] (3) (where [PN(3)] = PhPMe(CHSiMe(2)NSiMe(2)CH(2)P(Ph)CH(2)SiMe(2)NSiMe(2)N)). Complex 3 has been characterized

  [P(2)N(2)]NbCl (其中 [P(2)N(2)] = PhP(CH(2)SiMe(2)NSiMe(2)CH(2))(2)PPh 的还原) 与 KC(8) 在二氮气氛下生成顺磁性双核二氮复合物 ([P(2)N(2)]Nb)(2)(mu-N(2)) (2)。复合物 2 已通过晶体学和 EPR 光谱进行表征。变温磁化率测量表明 2 显示两个 Nb(IV) (d(1​​)) 中心之间的反铁磁耦合。对模型复合体 [(PH(3))(2)(NH(2))(2)Nb](2)(mu-N(2)) 进行了密度泛函理论计算。([P(2)N(2)]Nb)(2)(mu-N(2)) 在甲苯中的热解产生顺磁性桥接氮化物物种，其中二氮配体的一个 N 原子插入大环骨架形成 [ P(2)N(2)]Nb(mu-N)Nb[PN(3)] (3) （其中 [PN(3)] = PhPMe(CHSiMe(2)NSiMe(2)CH(2)P(
• Dinuclear organometallic dinitrogen complexes of niobium
  作者：Michael D Fryzuk、Christopher M Kozak、Brian O Patrick

  DOI：10.1016/s0020-1693(02)01305-1

  日期：2003.3

  The niobium(III) chloride precursors (R)[P2N2]NbCl stabilized by the bis-(amidophosphine) macrocycle (where (R)[P2N2] RP(CH2SiMe2NSiMe2CH2)(2)PR, R = phenyl, Ph, or cyclohexyl, Cy), react with MeMgCl under argon to form the paramagnetic (R)[P2N2]NbMe (R = Ph, 1; R = Cy, 2) complexes. The methyl complexes I and 2 can be stabilized by the donor solvent pyridine to form the paramagnetic adducts R [P2N2]NbMe(py) (R = Ph, 3; R = Cy, 4). Methyl complexes 1 and 2 readily react with N-2 to form the diamagnetic dinuclear dinitrogen compounds, (R[P2N2]NbMe)(2)(mu-N-2) (R = Ph, 5; R = Cy, 6), which have been characterized crystallographically. Dinitrogen complex 5 is fluxional and undergoes enantiomeric inversion of the six-coordinate niobium centres via axial rotation about the Nb-N-2-Nb axis. Complex 6 shows no enantiomeric inversion, likely due to the steric effects of the cyclohexyl substituents. The dinitrogen ligand itself is labile at elevated temperatures and undergoes reversible dissociation; the dinitrogen complexes are reformed upon cooling to room temperature. Reaction of 5 and 6 with CO displaces the N-2 fragment forming the bridging acyl complexes (R [P2N2]Nb)(2)(mu-COCH3)(2) (R = Ph, 7; R = Cy, 8) where the carbonyl fragments bond to the metal centres in a eta(2) fashion. Addition of H-2 to 5 and 6 results in the formation of the previously reported paramagnetic dinuclear dinitrogen complex, ((R)[P2N2]Nb)(2)(mu-N-2). (C) 2002 Elsevier Science B.V. All rights reserved.