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Volumn 30, Issue 3, 2011, Pages 520-527

Kinetics and mechanism of molybdenum-mediated acrylate formation from carbon dioxide and ethylene

Author keywords

[No Author keywords available]

Indexed keywords

ACTIVATION PARAMETER; C-C BOND FORMATION; FUNCTIONALIZATIONS; HYDRIDE COMPLEXES; HYDRIDE ELIMINATION; ISOTOPE EFFECT; ISOTOPIC LABELING; KINETICS AND MECHANISM; MOLYBDENUM COMPLEX; RATE LIMITING; REACTION PATHWAYS; TEMPERATURE RANGE; ZEROVALENT;

EID: 79751489881     PISSN: 02767333     EISSN: 15206041     Source Type: Journal    
DOI: 10.1021/om100891m     Document Type: Article
Times cited : (58)

References (68)
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    • United States Department of Enery. Energy Information Administration, International Energy Annual 2010. July; EIA-0484.
    • United States Department of Enery. Energy Information Administration, International Energy Annual 2010. July 2010; EIA-0484.
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    • ICIS Market Research Report,; Reported February; (accessed July 22, 2010).
    • ICIS Market Research Report, Acrylic Acid Uses and Market Data; Reported February 2010; http://www.icis.com/v2/chemicals/9074864/acrylic-acid.html (accessed July 22, 2010).
    • (2010) Acrylic Acid Uses and Market Data
  • 36
    • 79751469665 scopus 로고    scopus 로고
    • Incorporation of a bidentate phosphine into Carmona's molybdenum complexes did not produce clean acrylate formation, although coupling was successful with bidentate tungsten species (ref 17c).
    • Incorporation of a bidentate phosphine into Carmona's molybdenum complexes did not produce clean acrylate formation, although coupling was successful with bidentate tungsten species (ref 17c).
  • 50
    • 79751517100 scopus 로고    scopus 로고
    • See Supporting Information.
    • See Supporting Information.
  • 51
    • 0030227105 scopus 로고    scopus 로고
    • For a representative paper addressing the stereochemistry of seven-coordinate metals see
    • For a representative paper addressing the stereochemistry of seven-coordinate metals see: Fay, R. C. Coord. Chem. Rev. 1996, 154, 99
    • (1996) Coord. Chem. Rev. , vol.154 , pp. 99
    • Fay, R.C.1
  • 53
    • 79751499208 scopus 로고    scopus 로고
    • -1
    • -1.
  • 56
    • 64549144220 scopus 로고    scopus 로고
    • For examples of other formally five-coordinate molybdenum(0) complexes see: ref 24f and
    • For examples of other formally five-coordinate molybdenum(0) complexes see: ref 24f and Niikura, F.; Seino, H.; Mizobe, Y. Organometallics 2009, 28, 1112
    • (2009) Organometallics , vol.28 , pp. 1112
    • Niikura, F.1    Seino, H.2    Mizobe, Y.3
  • 60
    • 79751511690 scopus 로고    scopus 로고
    • 2 addition may also influence the rate of conversion to 4, obscuring firm conclusions regarding inhibition by dinitrogen.
    • 2 addition may also influence the rate of conversion to 4, obscuring firm conclusions regarding inhibition by dinitrogen.
  • 61
    • 79751485375 scopus 로고    scopus 로고
    • Less than 15% formation of 2 was observed prior to complete conversion of 1 to 4.
    • Less than 15% formation of 2 was observed prior to complete conversion of 1 to 4.
  • 62
    • 79751471148 scopus 로고    scopus 로고
    • The C-C bond forming event may also be viewed as a nucleophilic attack by ethylene on the electrophilic carbon dioxide.
    • The C-C bond forming event may also be viewed as a nucleophilic attack by ethylene on the electrophilic carbon dioxide.
  • 63
    • 79751485988 scopus 로고    scopus 로고
    • A third possibility, rate-limiting dimerization, is deemed unlikely given that the absence of observable acrylate hydride monomer necessitates two rapid equilibria between 4-metallalactone and metallalactone-acylate hydride monomer, both of which must favor the reactants. This possibility is also excluded on the basis of the measured KIE and activation entropy.
    • A third possibility, rate-limiting dimerization, is deemed unlikely given that the absence of observable acrylate hydride monomer necessitates two rapid equilibria between 4-metallalactone and metallalactone-acylate hydride monomer, both of which must favor the reactants. This possibility is also excluded on the basis of the measured KIE and activation entropy.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.