Olefin metathesis for metal incorporation: Preparation of conjugated ruthenium-containing complexes and polymers

Sarah L. Bolton, Danielle E. Schuehler, Xiang Niu, Lakshmi Gopal, Michael Sponsler

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

Olefin Metathesis for Metal Incorporation (OMMI) was used for the stoichiometric attachment of ruthenium to both small and large polyenes. The dinuclear complexes (PCy3)2C12Ru{double bond, long}CH(CH{double bond, long}CH)nCH{double bond, long}Ru(PCy3)2Cl2 (n = 1, 2), were prepared by reacting 2 equiv. of the Grubbs first-generation catalyst (PCy3)2C12Ru{double bond, long}(CHPh)) with 1 equiv. of the appropriate polyene (1,3,5-hexatriene for n = 1 and 1,3,5,7-octatetraene for n = 2). Use of excess hexatriene led to the formation of the monoruthenium complex (PCy3)2C12Ru{double bond, long}CHCH{double bond, long} CHCH{double bond, long}CH2. The mono- and di-ruthenium complexes exhibited marked differences in their spectroscopic and electrochemical properties, in addition to their Z-E isomerization rates. Nucleophilic attack of PCy3 on the end CH2 of the mono complex was observed, leading to both isomerization and phosphonium products. Extending the OMMI strategy to the second-generation catalyst was also done, despite the reduced initiation rate. The more reactive catalyst (H2IMes)RuCl2({double bond, long}CHPh)(3-bromopyridine)2 allowed for ruthenium incorporation into polyacetylene, leading to the formation of polymers and oligomers with high ruthenium content.

Original languageEnglish (US)
Pages (from-to)5298-5306
Number of pages9
JournalJournal of Organometallic Chemistry
Volume691
Issue number24-25
DOIs
StatePublished - Dec 1 2006

Fingerprint

Ruthenium
metathesis
Alkenes
ruthenium
alkenes
Olefins
Polymers
Metals
preparation
polymers
Polyenes
metals
methylidyne
Isomerization
catalysts
isomerization
Catalysts
Polyacetylenes
polyacetylene
Electrochemical properties

Keywords

  • Alkylidene
  • Olefin metathesis
  • Ruthenium

ASJC Scopus subject areas

  • Biochemistry
  • Chemical Engineering (miscellaneous)
  • Inorganic Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Science (miscellaneous)
  • Materials Chemistry

Cite this

Olefin metathesis for metal incorporation : Preparation of conjugated ruthenium-containing complexes and polymers. / Bolton, Sarah L.; Schuehler, Danielle E.; Niu, Xiang; Gopal, Lakshmi; Sponsler, Michael.

In: Journal of Organometallic Chemistry, Vol. 691, No. 24-25, 01.12.2006, p. 5298-5306.

Research output: Contribution to journalArticle

Bolton, Sarah L. ; Schuehler, Danielle E. ; Niu, Xiang ; Gopal, Lakshmi ; Sponsler, Michael. / Olefin metathesis for metal incorporation : Preparation of conjugated ruthenium-containing complexes and polymers. In: Journal of Organometallic Chemistry. 2006 ; Vol. 691, No. 24-25. pp. 5298-5306.
@article{0c9d894c60eb455c86f2cb027c71dd16,
title = "Olefin metathesis for metal incorporation: Preparation of conjugated ruthenium-containing complexes and polymers",
abstract = "Olefin Metathesis for Metal Incorporation (OMMI) was used for the stoichiometric attachment of ruthenium to both small and large polyenes. The dinuclear complexes (PCy3)2C12Ru{double bond, long}CH(CH{double bond, long}CH)nCH{double bond, long}Ru(PCy3)2Cl2 (n = 1, 2), were prepared by reacting 2 equiv. of the Grubbs first-generation catalyst (PCy3)2C12Ru{double bond, long}(CHPh)) with 1 equiv. of the appropriate polyene (1,3,5-hexatriene for n = 1 and 1,3,5,7-octatetraene for n = 2). Use of excess hexatriene led to the formation of the monoruthenium complex (PCy3)2C12Ru{double bond, long}CHCH{double bond, long} CHCH{double bond, long}CH2. The mono- and di-ruthenium complexes exhibited marked differences in their spectroscopic and electrochemical properties, in addition to their Z-E isomerization rates. Nucleophilic attack of PCy3 on the end CH2 of the mono complex was observed, leading to both isomerization and phosphonium products. Extending the OMMI strategy to the second-generation catalyst was also done, despite the reduced initiation rate. The more reactive catalyst (H2IMes)RuCl2({double bond, long}CHPh)(3-bromopyridine)2 allowed for ruthenium incorporation into polyacetylene, leading to the formation of polymers and oligomers with high ruthenium content.",
keywords = "Alkylidene, Olefin metathesis, Ruthenium",
author = "Bolton, {Sarah L.} and Schuehler, {Danielle E.} and Xiang Niu and Lakshmi Gopal and Michael Sponsler",
year = "2006",
month = "12",
day = "1",
doi = "10.1016/j.jorganchem.2006.08.085",
language = "English (US)",
volume = "691",
pages = "5298--5306",
journal = "Journal of Organometallic Chemistry",
issn = "0022-328X",
publisher = "Elsevier",
number = "24-25",

}

TY - JOUR

T1 - Olefin metathesis for metal incorporation

T2 - Preparation of conjugated ruthenium-containing complexes and polymers

AU - Bolton, Sarah L.

AU - Schuehler, Danielle E.

AU - Niu, Xiang

AU - Gopal, Lakshmi

AU - Sponsler, Michael

PY - 2006/12/1

Y1 - 2006/12/1

N2 - Olefin Metathesis for Metal Incorporation (OMMI) was used for the stoichiometric attachment of ruthenium to both small and large polyenes. The dinuclear complexes (PCy3)2C12Ru{double bond, long}CH(CH{double bond, long}CH)nCH{double bond, long}Ru(PCy3)2Cl2 (n = 1, 2), were prepared by reacting 2 equiv. of the Grubbs first-generation catalyst (PCy3)2C12Ru{double bond, long}(CHPh)) with 1 equiv. of the appropriate polyene (1,3,5-hexatriene for n = 1 and 1,3,5,7-octatetraene for n = 2). Use of excess hexatriene led to the formation of the monoruthenium complex (PCy3)2C12Ru{double bond, long}CHCH{double bond, long} CHCH{double bond, long}CH2. The mono- and di-ruthenium complexes exhibited marked differences in their spectroscopic and electrochemical properties, in addition to their Z-E isomerization rates. Nucleophilic attack of PCy3 on the end CH2 of the mono complex was observed, leading to both isomerization and phosphonium products. Extending the OMMI strategy to the second-generation catalyst was also done, despite the reduced initiation rate. The more reactive catalyst (H2IMes)RuCl2({double bond, long}CHPh)(3-bromopyridine)2 allowed for ruthenium incorporation into polyacetylene, leading to the formation of polymers and oligomers with high ruthenium content.

AB - Olefin Metathesis for Metal Incorporation (OMMI) was used for the stoichiometric attachment of ruthenium to both small and large polyenes. The dinuclear complexes (PCy3)2C12Ru{double bond, long}CH(CH{double bond, long}CH)nCH{double bond, long}Ru(PCy3)2Cl2 (n = 1, 2), were prepared by reacting 2 equiv. of the Grubbs first-generation catalyst (PCy3)2C12Ru{double bond, long}(CHPh)) with 1 equiv. of the appropriate polyene (1,3,5-hexatriene for n = 1 and 1,3,5,7-octatetraene for n = 2). Use of excess hexatriene led to the formation of the monoruthenium complex (PCy3)2C12Ru{double bond, long}CHCH{double bond, long} CHCH{double bond, long}CH2. The mono- and di-ruthenium complexes exhibited marked differences in their spectroscopic and electrochemical properties, in addition to their Z-E isomerization rates. Nucleophilic attack of PCy3 on the end CH2 of the mono complex was observed, leading to both isomerization and phosphonium products. Extending the OMMI strategy to the second-generation catalyst was also done, despite the reduced initiation rate. The more reactive catalyst (H2IMes)RuCl2({double bond, long}CHPh)(3-bromopyridine)2 allowed for ruthenium incorporation into polyacetylene, leading to the formation of polymers and oligomers with high ruthenium content.

KW - Alkylidene

KW - Olefin metathesis

KW - Ruthenium

UR - http://www.scopus.com/inward/record.url?scp=33751237372&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33751237372&partnerID=8YFLogxK

U2 - 10.1016/j.jorganchem.2006.08.085

DO - 10.1016/j.jorganchem.2006.08.085

M3 - Article

AN - SCOPUS:33751237372

VL - 691

SP - 5298

EP - 5306

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

IS - 24-25

ER -