• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to previous page

Preparation of Multinuclear Complexes by a Ring-Opening Reaction of a Highly Strained Cyclic Ferrocene Unit and Their Reactivity

Research Project

Project/Area Number 13640560
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic chemistry
Research InstitutionHIROSHIMA UNIVERSITY

Principal Investigator

MIZUTA Tsutomu  Hiroshima Univ., Graduate School of Science, Associate Professor, 大学院・理学研究科, 助教授 (70221603)

Project Period (FY) 2001 – 2002
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥3,500,000 (Direct Cost: ¥3,500,000)
Fiscal Year 2002: ¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 2001: ¥1,900,000 (Direct Cost: ¥1,900,000)
Keywordsferrocenophane / strained phosphorus compound / ring-opening reaction / photolysis / ferrocence / macrocyclic ligend / ring slippage / multinuclear complex / ヘテロ多核錯体 / P-C結合解裂 / 光重合
Research Abstract

In this project, PhP-bridged [1] ferrocenophane (1) was utilized as a ligand having functionality for construction of multinuclear framework, because a single-atom-bridged [1] ferrocenophane readily undergoes a ring-opening reaction owing to its highly strained ring structure.
When 1 or its sulfuriezed derivative is irradiated by UV-V is light in THF or CH_3CN, ring-opening polymerization takes place to give a polyferrocene derivative and trimers and dimers both of which have macrocyclic structures. A reaction mechanism was investigated for this ring-opening reaction, and was proposed as follows. 1), irradiation of 1 gives a ring-slipped product (2) in which one of the two Cp rings changes its coordination mode from n^5 to n^1. 2), the n^1-Cp of 2 attacks an iron center of another 2. 3), a ferrocene unit is reproduced and the n^1-Cp originally on the iron center of the letter 2 is expelled from the iron center. 4), a polyferrocene framework is propagated by repetition of the steps 1-3.
A reaction of Pt(PMe_3)_4 with 1 coordinating to CpMn(CO)_2 and W(CO)_5 fragments gives heterodinuclear complexes (actually they are triangular complexes if an iron center of a ferrocene unit is included), in which a Pt(Pme_3)_2 fragment is inserted into a P-Cp bond of 1 to form P-Pt and N^1-C_5H_4-Pt bounds with a u-PPhFc bridge (u-PPhFc=u-PPh(C_5H_4FeC_5H_4)). X-ray analyses showed that the products are Cp(CO)_2Mn(u-PPhFc)Pt(Pme_3)_2 and(CO)_%W(uPPhFc)Pt(Pme_3)_2, respectively. Upon a similar reaction employing Pt(PPh_3)_4 in place of Pt(Pme_3)_4, CpMn(CO)\2(1) gives Cp(CO)Mn(u-CO)(u-PPhFc)Pt(PPh_3), whereas W(CO)_5(1) gives (CO)_4W(u-PPh_2)(u-PPh(C_5H_4FeC_5H_4H_4Ph))Pt(PPh_3), in which cleavage of a P-Ph bond of PPh_3 and migration of the Ph group to a ferrocene moiety take place.

Report

(3 results)
  • 2002 Annual Research Report   Final Research Report Summary
  • 2001 Annual Research Report
  • Research Products

    (24 results)

All Other

All Publications (24 results)

  • [Publications] H.Nakazawa: "Conversion of a stannyl-phosphenium complex into a stannylene-phosphine complex of Mo and W : double bond migration from M=P to M=Sn"J. Organomet. Chem.. 617-618. 453-463 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Mizuta: "Naphtho[1,8-b, c]phosphete and 1,2-Diphosphaacenaphthene from the Reaction of 1,8-Dilithionaphthalene with RPCl_2"Angew. Chem. Int. Ed.. 41. 3897-3898 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Mizuta: "Reactivity of Heterodinuclear Complexes Formed by Platinum Insertion to Phosphorus-Bridged [1]Ferrocenophane Coordinating to a Metal Fragment"Organometallics. 21. 717-726 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Mizuta: "Interaction modes with a halide anion of metal centers of edge-sharing dinuclear complexes bearing a bent form"Bull. Chem. Soc. Jpn.. 75. 1547-1552 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Mizuta: "Addition of phenylacetylene to a P-C bond of phosphorus-bridged [1]ferrocenophane"Phosphorus, Sulfur, and Silicon. 177. 2157-2158 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K.Kubo: "Preparation of metallaiminophosphoranes and their reactivity"Phosphorus, Sulfur, and Silicon. 177. 2159-2160 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] J.Ushio: "1,2-addition of diphosphine monoxide to a double bond of a titanocene carbene complex"Phosphorus, Sulfur, and Silicon. 177. 2167-2168 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Mizuta: "Ring-Opening Reaction of Phosphorus-Bridged [1]ferrocenophane via Ring Slippage from η5-to η1-Cp"J. Am. Chem. Soc.. 125. 2068-2069 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Ishiyama: "Formation of novel phosphide dichloride Zr complex from trichloride Zr complex with a secondary phosphine-pendant cyclopentadienyl ligand : Structure of [{η5-C_5H_4(CH_2)_2PMes-κP)ZrCl_2(N-methylimidazole)_2] (Mes=2,4,6-trimethylphenyl)"Chem. Lett.. 32. 70-71 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] H. Nakazawa, M. Kishishita, T. Ishiyama, T. Mizuta, K. Miyashi: "Conversion of a stannyl-phosphenium complex into a stannylene-phosphine complex of Mo and W: double bond migration from M=P to M=Sn"J. Organomet. Chem.. 617-618, 453-463 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T. Mizuta, T. Nakazono, K. Miyoshi: "Naphtho[1,8-b, c]phosphate and 1,2-Diphosphaacenaphthene from the Reaction of 1, 8-Dilithionaphthalene with RPCI_2"Angew. Chem. Int. Ed.,. 41. 3897-3898 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T. Mizuta, M. Onishi, T. Nakasono, H. Nakazawa, K.Miyoshi: "Reactivity of Heterodinuclear Complexes Formed by Platinum Insertion to Phosphorus-Bridged [1] Ferrocenophane Coordinating to a Metal Fragment"Organometallics. 21. 717-726 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T. Mizuta, K. Nakayama, S. Aoki, K. Miyoshi: "Interaction modes with a halide anion of metal centers of edge-sharing dinuclear complexes bearing a bent form"Bull. Chem. Soc. Jpn.. 75. 1547-1552 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T. Mizuta, M. Onishi, T. Nakazono, H. Nakazawa, K. Miyoshi: "Addition of phenylacety to a P-C bond of phosphorus-bridged [1] ferrocenophane"Phosphorus, Sulfur, and Silicon. 177. 2157-2158 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K. Kubo, H. Nakazawa, H. Inagaki, T. Miyake, T. Mizuta, K. Miyoshi: "Preparation of metallaiminophosphoranes and their reactivity"Phosphorus, Sulfur, and Silicon. 177. 2159-2168 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] J. Ushio, H. Murakami, T. Mizuta, K. Miyoshi: "1,2-addition of diphosphine monoxide to a double baud of a titanocene carbine complex"Phosphorus, Sulfur, and Silicon. 177. 2167-2168 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T. Mizuta, Y. Imamura, K. Miyoshi: "Ring-Opening Reaction of Phosphorus-Bridged [1] ferrocenophane via Ring Slippage from n5-to n1-Cp"J. Am. Chem. Soc.. 125. 2068-2069 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T. Ishiyama, T. Mizuta, K. Miyoshi, H. Nakazawa: "Formation of novel phosphide dichloride Zr complex from trichloride Zr complex with a secondary phosphine-pendant cyclopentadieny ligand: Structure of [{n5-C_5H_4(CH_2)_2PMes-kP)ZrCl_2(N-methylimidazole)_2](Mes=2,4,6-trimethylphenyl)"Chem. Lett.. 32. 70-71 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Mizuta, T.Nakazono, K.Miyoshi: "Naphtho[1,8-b, c]phosphete and 1,2-Diphosphaacenaphthene from the Reaction of 1,8-Dilithionaphthalene with RPCl_2"Angew. Chem. Int. Ed.. 41. 3897-3898 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] T.Mizuta, K.Nakayama, S.Aoki, K.Misyoshi: "Interaction modes with a halide anion of metal centers of edge-sharing dinuclear complexes bearing a bent form"Bull. Chem. Soc. Jpn.. 75. 1547-1552 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] T.Mizuta, M.Onishi, T.Nakazono, H.Nakazawa, K.Miyoshi: "Addition of phenylacetylene to a P-C bond of phosphorus-bridged [1]ferrocenophane"Phosphorus, Sulfur, and Silicon. 177. 2157-2158 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] T.Mizuta, Y.Imamura, K.Miyoshi: "Ring-Opening Reaction of Phosphorus-Bridged [1]ferrocenophane via Ring Slippage from η^5-to η^1-Cp"J. Am. Chem. Soc.. 125. 2068-2069 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] Hiroshi Nakazawa: "Conversion of a stannyl-phosphenium complex into a stannylene-phosphine complex of Mo and W: double bond migration from M=P to M=Sn"I. Organomet. Chem.. 617-618. 453-463 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Tsutomu Mizuta: "Reactivity of Heterodinuclear Complexes Formed by Platinum Insertion to Phosphorus-Bridged [1]Ferrocenophane Coordinating to a Metal Fragment"Organometallics. 21. 717-726 (2002)

    • Related Report
      2001 Annual Research Report

URL: 

Published: 2001-04-01   Modified: 2016-04-21  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi