[(η(5)-C5EtMe4)2ZrCl(PH(cyclohexyl))] | 192864-30-5

• 英文名称: [(η(5)-C5EtMe4)2ZrCl(PH(cyclohexyl))]
• CAS: 192864-30-5
• 化学式: C₂₈H₄₆ClPZr
• 分子量: 540.324
• InChiKey: LILDURQCZGLMGH-UHFFFAOYSA-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：

  [(η(5)-C5EtMe4)2ZrCl(PH(cyclohexyl))] 、 异氰酸异丙酯 以 正戊烷 为溶剂， 以85%的产率得到
  参考文献：
  名称：

  Formation of Novel P-Functionalized Ligands by Insertion Reactions of RNCX (R = Ph, X = O, S; R = Prⁱ, X = O) into the Zr−P Bond of [Cp°₂ZrCl(PHCy)] (Cp° = η⁵-C₅EtMe₄, Cy = Cyclohexyl) and [Cp‘₂ZrCl{PH(TRIP)}] (Cp‘ = η⁵-C₅MeH₄, TRIP = 2,4,6-Prⁱ₃C₆H₂)

  摘要：

  [Cp degrees(2)ZrCl(PHCy)] (1; Cp degrees = eta(5)-C5EtMe4, Cy = cyclohexyl) and [Cp'2ZrCl{PH(TRIP)}] (2; Cp' = eta(5)-C5MeH4,TRIP = 2,4,6-(Pr3C6H2)-C-i) readily insert RNCX (R = Ph, X = S, O; R = Pr-i, X = O) to give [Cp degrees(2)ZrCl{eta(2)-XC(PHCy)NR}] (X = S, R = - Ph (3); X = O, R = Ph (4); X = O, R = Pr-i (5)) and [ Cp'2ZrCl{eta(2)-XC{PH(TRTP)}NR}] (X = S, R = Ph (6); X = O; R = Ph (7); X = O, R = Pr-i (8)). 3-8 were characterized spectroscopically (IR, NMR, MS), and crystal structure determinations on 4-6 showed an eta(2) bonding mode (X,N) of the XC(PHR')NR (R' = Cy, TRIP) ligands. Of the two possible coordination modes of the ligand, 4 and 5 are obtained exclusively as the endo isomer, in which the NR group is adjacent to the Zr-Cl bond, while for 6-8, both isomers (endo and exo) are formed (1:8 (6), 1:30 (7) and 1:5 (8)), whereby the exo isomer is favored. The exo isomer of 6 was structurally characterized.

  DOI：

  10.1021/om000170k
• 作为产物：
  描述：

  bis(η5-tetramethylethylcyclopentadienyl)zirconium dichloride 、 lithium cyclohexylphosphanide 以 乙二醇二甲醚 为溶剂， 以77%的产率得到[(η(5)-C5EtMe4)2ZrCl(PH(cyclohexyl))]
  参考文献：
  名称：

  Formation of Novel P-Functionalized Ligands by Insertion Reactions of RNCX (R = Ph, X = O, S; R = Prⁱ, X = O) into the Zr−P Bond of [Cp°₂ZrCl(PHCy)] (Cp° = η⁵-C₅EtMe₄, Cy = Cyclohexyl) and [Cp‘₂ZrCl{PH(TRIP)}] (Cp‘ = η⁵-C₅MeH₄, TRIP = 2,4,6-Prⁱ₃C₆H₂)

  摘要：

  [Cp degrees(2)ZrCl(PHCy)] (1; Cp degrees = eta(5)-C5EtMe4, Cy = cyclohexyl) and [Cp'2ZrCl{PH(TRIP)}] (2; Cp' = eta(5)-C5MeH4,TRIP = 2,4,6-(Pr3C6H2)-C-i) readily insert RNCX (R = Ph, X = S, O; R = Pr-i, X = O) to give [Cp degrees(2)ZrCl{eta(2)-XC(PHCy)NR}] (X = S, R = - Ph (3); X = O, R = Ph (4); X = O, R = Pr-i (5)) and [ Cp'2ZrCl{eta(2)-XC{PH(TRTP)}NR}] (X = S, R = Ph (6); X = O; R = Ph (7); X = O, R = Pr-i (8)). 3-8 were characterized spectroscopically (IR, NMR, MS), and crystal structure determinations on 4-6 showed an eta(2) bonding mode (X,N) of the XC(PHR')NR (R' = Cy, TRIP) ligands. Of the two possible coordination modes of the ligand, 4 and 5 are obtained exclusively as the endo isomer, in which the NR group is adjacent to the Zr-Cl bond, while for 6-8, both isomers (endo and exo) are formed (1:8 (6), 1:30 (7) and 1:5 (8)), whereby the exo isomer is favored. The exo isomer of 6 was structurally characterized.

  DOI：

  10.1021/om000170k

文献信息

• Insertion of Acetonitrile into the Zr−P Bond of [Cp°₂ZrCl(PHCy)] (Cy = Cyclohexyl, Cp° = η⁵-C₅EtMe₄) Followed by PHCy Elimination To Give [Cp°₂(Cl)Zr(μ-NCMe−CMeN)Zr(Cl)Cp°₂]
  作者：Ulrike Segerer、Steffen Blaurock、Joachim Sieler、Evamarie Hey-Hawkins

  DOI：10.1021/om9901271

  日期：1999.7.1

  [Cp(2)degrees ZrCl(PHCy)] (Cy = cyclohexyl, Cp degrees = eta(5)-C5EtMe4) undergoes insertion of MeCN into the Zr-P bond, yielding [Cp(2)degrees ZrClN=C(Me)(PHCy)}] (1). Isomers with a Z (1a) or E (1b) configuration at the C-N double bond are obtained in a ratio of 13:1. At room temperature, 1 slowly decomposes in solution with elimination of a PHCy fragment and formation of [Cp(2)degrees(Cl)Zr(mu-N=CMe-CMe=N)Zr(Cl)Cp(2)degrees] (2). Two isomers are obtained with a trans (2a) or cis (2b) arrangement around the C-N double bonds of the bridging butane-2,3-diimino(2-)-N,N' ligand. 1a, 2a, and 2b were isolated and characterized by IR, MS, and NMR spectroscopy (H-1, P-31, C-13), and crystal structure determinations were carried out on 1a and 2a. In the solid state, the short Zr-N bonds and the almost linear Zr-N-C angles of 1a and 2a indicate the presence of Zr-N double bonds.
• Formation of novel P-functionalised ligands by insertion of CyNC into the ZrP bonds of [Cp°2ZrCl(PHCy)] (Cp°=η5-C5EtMe4, Cy=cyclohexyl) and [Cp′2ZrCl(PHTipp)] (Cp′=η5-C5H4Me, Tipp=2,4,6-Pri3C6H2). Molecular structures of [Cp°2ZrCl{η2-NCyC(PHCy)}] and [Cp′2Zr(Cl){η2-NCyC(PHTipp)}]
  作者：Ulrike Segerer、Steffen Blaurock、Joachim Sieler、Evamarie Hey-Hawkins

  DOI：10.1016/s0022-328x(00)00313-2

  日期：2000.8

  [Cp'2ZrCl(PHTipp)] (1) (Cp' = eta(5)-C5H4Me, Tipp = 2,4,6-Pr'3C6H2) and [(Cp2ZrCl)-Zr-o(PHCy)] (2) (Cp-o = eta(5)-C5EtMe4, Cy = cyclohexyl) readily insert CyNC to give [Cp'2ZrCleta(2)-NCyC(PHTipp)}] (3) and [(Cp2ZrCl)-Zr-oeta(2)-NCyC(PHCy)}] (4). 3 and 4 were characterised spectroscopically (IR, NMR, MS) and by crystal structure determination, which showed an eta(2) bonding mode (C,N) of the NCyC(PHR) ligands. Of the two possible coordination modes of the ligand, 3 is obtained exclusively as the exo isomer, in which the NCy group is adjacent to the Zr-Cl bond, while for 4, both isomers (exo and endo) are formed [1:1.5 (4a:4b)], whereby the endo isomer is favoured. The exo isomer 4a was structurally characterised. (C) 2000 Elsevier Science S.A. All rights reserved.
• Formation of novel P-functionalized ligands by insertion reactions into the ZrP bond of Cp2°ZrCl(PHCy) (Cp°η5-C5EtMe4 Cy = cyclohexyl)
  作者：Ulrike Segerer、Evamarie Hey-Hawkins

  DOI：10.1016/s0277-5387(97)00001-6

  日期：1997.1

  Cp-2 degrees ZrCl2 (Cp degrees = eta(5)-C5EtMe4) reacts with LiPHCy (Cy = cyclohexyl) with the formation of Cp-2 degrees ZrCl(PHCy) (1). Compound 1 undergoes insertion of CS2 or PhNCS into the Zr-P bond, yielding Cp-2 degrees ZrCl(eta(2)-S2CPHCy) (2) and Cp-2 degrees ZrCleta(2)-SC(PHCY)NPh} (3). Compounds 1-3 were characterized spectroscopically (IR, NMR, MS) and crystal structure determinations were carried out on 1 and 3, showing an eta(2)-bonding mode of the SC(PHCy)NPh (S, N) ligand in the latter. (C) 1997 Elsevier Science Ltd.