Evaluation of molybdenum and tungsten metathesis catalysts for homogeneous tandem alkane metathesis

Brad C. Bailey, Richard R. Schrock, Sabuj Kundu, Alan S Goldman, Zheng Huang, Maurice Brookhart

Research output: Contribution to journalArticle

67 Citations (Scopus)

Abstract

Over 40 molybdenum and tungsten imido alkylidene mono(alkoxide) mono(pyrrolide) (MAP) or bis(alkoxide) olefin metathesis catalysts were examined in combination with Ir-based pincer-type catalysts for the metathesis of n-octane. The imido group, alkoxide, and metal in the metathesis catalysts were all found to be important variables. The best catalyst was W(NAr)(CHR) (OSiPh 3) 2 (Ar = 2,6-diisopropy-lphenyl), which performed about twice as well as the only previously employed catalyst, Mo(NAr)(CH-R)[OCMe(CF 3) 2] 2. Product yields decreased at temperatures greater than 125 °C, most likely because of the instability of the metathesis catalysts at such temperatures. POCOP Ir catalysts gave higher yields than PCP Ir catalysts, although the latter exhibited some selectivity for formation of tetradecane. Eight catalysts were synthesized in situ through addition of alcohols to bis(2,5-dimethylpyrrolide) complexes; in situ catalysts were shown to perform approximately as well as the isolated complexes, which suggests that 2,5-dimethylpyrrole is not detrimental to the alkane metathesis process and that potential catalysts can be screened more conveniently in this way.

Original languageEnglish
Pages (from-to)355-360
Number of pages6
JournalOrganometallics
Volume28
Issue number1
DOIs
Publication statusPublished - Jan 12 2009

Fingerprint

Tungsten
Alkanes
Molybdenum
metathesis
alkanes
molybdenum
tungsten
catalysts
Catalysts
evaluation
alkoxides
alkylidene
Catalyst selectivity
Alkenes
octanes
alkenes
alcohols
selectivity
Metals
Alcohols

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Evaluation of molybdenum and tungsten metathesis catalysts for homogeneous tandem alkane metathesis. / Bailey, Brad C.; Schrock, Richard R.; Kundu, Sabuj; Goldman, Alan S; Huang, Zheng; Brookhart, Maurice.

In: Organometallics, Vol. 28, No. 1, 12.01.2009, p. 355-360.

Research output: Contribution to journalArticle

Bailey, Brad C. ; Schrock, Richard R. ; Kundu, Sabuj ; Goldman, Alan S ; Huang, Zheng ; Brookhart, Maurice. / Evaluation of molybdenum and tungsten metathesis catalysts for homogeneous tandem alkane metathesis. In: Organometallics. 2009 ; Vol. 28, No. 1. pp. 355-360.
@article{a6feddc2bbb046d8836f3df1d9e20929,
title = "Evaluation of molybdenum and tungsten metathesis catalysts for homogeneous tandem alkane metathesis",
abstract = "Over 40 molybdenum and tungsten imido alkylidene mono(alkoxide) mono(pyrrolide) (MAP) or bis(alkoxide) olefin metathesis catalysts were examined in combination with Ir-based pincer-type catalysts for the metathesis of n-octane. The imido group, alkoxide, and metal in the metathesis catalysts were all found to be important variables. The best catalyst was W(NAr)(CHR) (OSiPh 3) 2 (Ar = 2,6-diisopropy-lphenyl), which performed about twice as well as the only previously employed catalyst, Mo(NAr)(CH-R)[OCMe(CF 3) 2] 2. Product yields decreased at temperatures greater than 125 °C, most likely because of the instability of the metathesis catalysts at such temperatures. POCOP Ir catalysts gave higher yields than PCP Ir catalysts, although the latter exhibited some selectivity for formation of tetradecane. Eight catalysts were synthesized in situ through addition of alcohols to bis(2,5-dimethylpyrrolide) complexes; in situ catalysts were shown to perform approximately as well as the isolated complexes, which suggests that 2,5-dimethylpyrrole is not detrimental to the alkane metathesis process and that potential catalysts can be screened more conveniently in this way.",
author = "Bailey, {Brad C.} and Schrock, {Richard R.} and Sabuj Kundu and Goldman, {Alan S} and Zheng Huang and Maurice Brookhart",
year = "2009",
month = "1",
day = "12",
doi = "10.1021/om800877q",
language = "English",
volume = "28",
pages = "355--360",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "1",

}

TY - JOUR

T1 - Evaluation of molybdenum and tungsten metathesis catalysts for homogeneous tandem alkane metathesis

AU - Bailey, Brad C.

AU - Schrock, Richard R.

AU - Kundu, Sabuj

AU - Goldman, Alan S

AU - Huang, Zheng

AU - Brookhart, Maurice

PY - 2009/1/12

Y1 - 2009/1/12

N2 - Over 40 molybdenum and tungsten imido alkylidene mono(alkoxide) mono(pyrrolide) (MAP) or bis(alkoxide) olefin metathesis catalysts were examined in combination with Ir-based pincer-type catalysts for the metathesis of n-octane. The imido group, alkoxide, and metal in the metathesis catalysts were all found to be important variables. The best catalyst was W(NAr)(CHR) (OSiPh 3) 2 (Ar = 2,6-diisopropy-lphenyl), which performed about twice as well as the only previously employed catalyst, Mo(NAr)(CH-R)[OCMe(CF 3) 2] 2. Product yields decreased at temperatures greater than 125 °C, most likely because of the instability of the metathesis catalysts at such temperatures. POCOP Ir catalysts gave higher yields than PCP Ir catalysts, although the latter exhibited some selectivity for formation of tetradecane. Eight catalysts were synthesized in situ through addition of alcohols to bis(2,5-dimethylpyrrolide) complexes; in situ catalysts were shown to perform approximately as well as the isolated complexes, which suggests that 2,5-dimethylpyrrole is not detrimental to the alkane metathesis process and that potential catalysts can be screened more conveniently in this way.

AB - Over 40 molybdenum and tungsten imido alkylidene mono(alkoxide) mono(pyrrolide) (MAP) or bis(alkoxide) olefin metathesis catalysts were examined in combination with Ir-based pincer-type catalysts for the metathesis of n-octane. The imido group, alkoxide, and metal in the metathesis catalysts were all found to be important variables. The best catalyst was W(NAr)(CHR) (OSiPh 3) 2 (Ar = 2,6-diisopropy-lphenyl), which performed about twice as well as the only previously employed catalyst, Mo(NAr)(CH-R)[OCMe(CF 3) 2] 2. Product yields decreased at temperatures greater than 125 °C, most likely because of the instability of the metathesis catalysts at such temperatures. POCOP Ir catalysts gave higher yields than PCP Ir catalysts, although the latter exhibited some selectivity for formation of tetradecane. Eight catalysts were synthesized in situ through addition of alcohols to bis(2,5-dimethylpyrrolide) complexes; in situ catalysts were shown to perform approximately as well as the isolated complexes, which suggests that 2,5-dimethylpyrrole is not detrimental to the alkane metathesis process and that potential catalysts can be screened more conveniently in this way.

UR - http://www.scopus.com/inward/record.url?scp=61849105359&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=61849105359&partnerID=8YFLogxK

U2 - 10.1021/om800877q

DO - 10.1021/om800877q

M3 - Article

VL - 28

SP - 355

EP - 360

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 1

ER -