Ruthenium/zirconium complexes containing C2 bridges with bond orders of 3, 2, and 1. Synthesis and structures of Cp(PMe3)2RuCHnHnZrClCp2 (n = 0, 1, 2)

Frederick R. Lemke, R Morris Bullock, R. Morris Bullock

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Abstract

A series of Ru/Zr complexes linked by C2 bridges of bond orders 3, 2, and 1 were prepared, and characterized by spectroscopic data and single-crystal X-ray diffraction. The dimetalloalkyne complex Cp(PMe3)2RuC≡CZrClCp2 was prepared by the reaction of Cp(PMe3)2RuC≡CH with either Cp2Zr(CH3)Cl or Cp2Zr(NMe2)Cl. This dimetalloalkyne is the first example of a structurally characterized alkyne that is substituted by an electron-rich metal at one end, and by an electron-deficient metal at the other. The reaction of Cp(PMe3)2RuC≡CH with [Cp2Zr(H)Cl]n gives the dimetalloalkene complex Cp(PMe3)2RuCH=CHZrClCp2, which has a three-center, two-electron agostic interaction between the Zr and the vinylic CH that is β to Zr. Carbonylation of Cp(PMe3)2RuCH=CHZrClCp2 with 1 atm of CO produces the η2-acyl complex Cp(PMe3)2RuCH=CHC(O)ZrClCp2. Analysis of the spectroscopic and structural data for this acyl compound indicates a substantial contribution from a zwitterionic resonance form that has a formal positive charge at Ru and a negative charge on the Zr portion. Hydrolysis of Cp(PMe3)2RuCH=CHZrClCp2 produces the known zirconium complex [Cp2ZrCl]2O and the ruthenium vinyl complex Cp(PMe3)2RuCH=CH2. Reaction of [Cp2Zr(H)Cl]n with Cp(PMe3)2RuCH=CH2 gives the dimetalloalkane complex Cp(PMe3)2RuCH2CH2ZrClCp2. Spectroscopic and crystallographic data are interpreted to indicate that this compound also has an agostic interaction between the Zr and a CH adjacent to Ru.

Original languageEnglish
Pages (from-to)8466-8477
Number of pages12
JournalJournal of the American Chemical Society
Volume113
Issue number22
Publication statusPublished - 1991

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Ruthenium
Zirconium
Electrons
Metals
Carbonylation
Alkynes
Carbon Monoxide
X-Ray Diffraction
Hydrolysis
Single crystals
X ray diffraction
Schwartz reagent

ASJC Scopus subject areas

  • Chemistry(all)

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@article{5d3f9d6d60204d3b8f02a179dd270ba9,
title = "Ruthenium/zirconium complexes containing C2 bridges with bond orders of 3, 2, and 1. Synthesis and structures of Cp(PMe3)2RuCHnHnZrClCp2 (n = 0, 1, 2)",
abstract = "A series of Ru/Zr complexes linked by C2 bridges of bond orders 3, 2, and 1 were prepared, and characterized by spectroscopic data and single-crystal X-ray diffraction. The dimetalloalkyne complex Cp(PMe3)2RuC≡CZrClCp2 was prepared by the reaction of Cp(PMe3)2RuC≡CH with either Cp2Zr(CH3)Cl or Cp2Zr(NMe2)Cl. This dimetalloalkyne is the first example of a structurally characterized alkyne that is substituted by an electron-rich metal at one end, and by an electron-deficient metal at the other. The reaction of Cp(PMe3)2RuC≡CH with [Cp2Zr(H)Cl]n gives the dimetalloalkene complex Cp(PMe3)2RuCH=CHZrClCp2, which has a three-center, two-electron agostic interaction between the Zr and the vinylic CH that is β to Zr. Carbonylation of Cp(PMe3)2RuCH=CHZrClCp2 with 1 atm of CO produces the η2-acyl complex Cp(PMe3)2RuCH=CHC(O)ZrClCp2. Analysis of the spectroscopic and structural data for this acyl compound indicates a substantial contribution from a zwitterionic resonance form that has a formal positive charge at Ru and a negative charge on the Zr portion. Hydrolysis of Cp(PMe3)2RuCH=CHZrClCp2 produces the known zirconium complex [Cp2ZrCl]2O and the ruthenium vinyl complex Cp(PMe3)2RuCH=CH2. Reaction of [Cp2Zr(H)Cl]n with Cp(PMe3)2RuCH=CH2 gives the dimetalloalkane complex Cp(PMe3)2RuCH2CH2ZrClCp2. Spectroscopic and crystallographic data are interpreted to indicate that this compound also has an agostic interaction between the Zr and a CH adjacent to Ru.",
author = "Lemke, {Frederick R.} and Bullock, {R Morris} and {Morris Bullock}, R.",
year = "1991",
language = "English",
volume = "113",
pages = "8466--8477",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "22",

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T1 - Ruthenium/zirconium complexes containing C2 bridges with bond orders of 3, 2, and 1. Synthesis and structures of Cp(PMe3)2RuCHnHnZrClCp2 (n = 0, 1, 2)

AU - Lemke, Frederick R.

AU - Bullock, R Morris

AU - Morris Bullock, R.

PY - 1991

Y1 - 1991

N2 - A series of Ru/Zr complexes linked by C2 bridges of bond orders 3, 2, and 1 were prepared, and characterized by spectroscopic data and single-crystal X-ray diffraction. The dimetalloalkyne complex Cp(PMe3)2RuC≡CZrClCp2 was prepared by the reaction of Cp(PMe3)2RuC≡CH with either Cp2Zr(CH3)Cl or Cp2Zr(NMe2)Cl. This dimetalloalkyne is the first example of a structurally characterized alkyne that is substituted by an electron-rich metal at one end, and by an electron-deficient metal at the other. The reaction of Cp(PMe3)2RuC≡CH with [Cp2Zr(H)Cl]n gives the dimetalloalkene complex Cp(PMe3)2RuCH=CHZrClCp2, which has a three-center, two-electron agostic interaction between the Zr and the vinylic CH that is β to Zr. Carbonylation of Cp(PMe3)2RuCH=CHZrClCp2 with 1 atm of CO produces the η2-acyl complex Cp(PMe3)2RuCH=CHC(O)ZrClCp2. Analysis of the spectroscopic and structural data for this acyl compound indicates a substantial contribution from a zwitterionic resonance form that has a formal positive charge at Ru and a negative charge on the Zr portion. Hydrolysis of Cp(PMe3)2RuCH=CHZrClCp2 produces the known zirconium complex [Cp2ZrCl]2O and the ruthenium vinyl complex Cp(PMe3)2RuCH=CH2. Reaction of [Cp2Zr(H)Cl]n with Cp(PMe3)2RuCH=CH2 gives the dimetalloalkane complex Cp(PMe3)2RuCH2CH2ZrClCp2. Spectroscopic and crystallographic data are interpreted to indicate that this compound also has an agostic interaction between the Zr and a CH adjacent to Ru.

AB - A series of Ru/Zr complexes linked by C2 bridges of bond orders 3, 2, and 1 were prepared, and characterized by spectroscopic data and single-crystal X-ray diffraction. The dimetalloalkyne complex Cp(PMe3)2RuC≡CZrClCp2 was prepared by the reaction of Cp(PMe3)2RuC≡CH with either Cp2Zr(CH3)Cl or Cp2Zr(NMe2)Cl. This dimetalloalkyne is the first example of a structurally characterized alkyne that is substituted by an electron-rich metal at one end, and by an electron-deficient metal at the other. The reaction of Cp(PMe3)2RuC≡CH with [Cp2Zr(H)Cl]n gives the dimetalloalkene complex Cp(PMe3)2RuCH=CHZrClCp2, which has a three-center, two-electron agostic interaction between the Zr and the vinylic CH that is β to Zr. Carbonylation of Cp(PMe3)2RuCH=CHZrClCp2 with 1 atm of CO produces the η2-acyl complex Cp(PMe3)2RuCH=CHC(O)ZrClCp2. Analysis of the spectroscopic and structural data for this acyl compound indicates a substantial contribution from a zwitterionic resonance form that has a formal positive charge at Ru and a negative charge on the Zr portion. Hydrolysis of Cp(PMe3)2RuCH=CHZrClCp2 produces the known zirconium complex [Cp2ZrCl]2O and the ruthenium vinyl complex Cp(PMe3)2RuCH=CH2. Reaction of [Cp2Zr(H)Cl]n with Cp(PMe3)2RuCH=CH2 gives the dimetalloalkane complex Cp(PMe3)2RuCH2CH2ZrClCp2. Spectroscopic and crystallographic data are interpreted to indicate that this compound also has an agostic interaction between the Zr and a CH adjacent to Ru.

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