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Volumn 15, Issue 24, 1996, Pages 5155-5165

Mechanistic investigation of stoichiometric alkyne insertion into Pt-B bonds and related chemistry bearing on the catalytic diborylation of alkynes mediated by platinum(II) diboryl complexes

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Indexed keywords


EID: 0001025292     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om960123l     Document Type: Article
Times cited : (164)

References (62)
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    • An excellent review of Pd-catalyzed cross-couplings of boronic acids has recently appeared: Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457-2483.
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    • Miyaura, N.1    Suzuki, A.2
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    • note
    • 3 by CatB-BCat was reported.
  • 31
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    • 30 bonds in the boryl-hydride complex derived from oxidative addition of catecholborane to Wilkinson's catalyst. Alkyne insertion into the Ir-H bond of an iridium hydridoboryl complex: Knorr, J. R.; Merola, J. S. Organometallics 1990, 9, 3008-3009.
    • (1990) Organometallics , vol.9 , pp. 3008-3009
    • Knorr, J.R.1    Merola, J.S.2
  • 32
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    • Associative pathways for alkyne insertion and alkene exchange have been proposed for Ni(II) and Pd(II) square-planar complexes: Gridnev, I. D.; Miyaura, N.; Suzuki, A. Organometallics 1993, 12, 589-592.
    • (1993) Organometallics , vol.12 , pp. 589-592
    • Gridnev, I.D.1    Miyaura, N.2    Suzuki, A.3
  • 35
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    • Phosphine dissociation in Pd(II) alkyl comlexes precedes alkyne insertion into Pd-C bonds: Samsel, E. G.; Norton, J. R. J. Am. Chem. Soc. 1984, 106, 5505-5512.
    • (1984) J. Am. Chem. Soc. , vol.106 , pp. 5505-5512
    • Samsel, E.G.1    Norton, J.R.2
  • 36
    • 33847089699 scopus 로고
    • Calculations predict that barriers for reductive elimination are lower for three-coordinate, 14 electron dialkyl complexes as opposed to square-planar 16 electron species. This has been confirmed experimentally.: Kominya, S.; Albright, T. A.; Hoffmann, R.; Kochi, J. K. J. Am. Chem. Soc. 1977, 99, 8440.
    • (1977) J. Am. Chem. Soc. , vol.99 , pp. 8440
    • Kominya, S.1    Albright, T.A.2    Hoffmann, R.3    Kochi, J.K.4
  • 40
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    • note
    • Boryl ligands are isolobal to carbene radical cations.
  • 41
    • 33847085021 scopus 로고
    • Experimental and theoretical work suggest that reductive elimination from a three-coordinate intermediate, such as 6, is reasonable. However, reductive elimination from square-planar Pt(II) complexes has been observed: Sen, A.; Halpern, J. Inorg. Chem. 1980, 19, 1073-1075.
    • (1980) Inorg. Chem. , vol.19 , pp. 1073-1075
    • Sen, A.1    Halpern, J.2
  • 42
    • 5244277498 scopus 로고    scopus 로고
    • note
    • 4-Octyne was diborylated under catalytic conditions. Once the reaction was complete, 3-hexyne was added to the reaction mixture and the solution was heated for 5 h at 80 °C. Diborylation of hexyne was not observed.
  • 44
    • 5244253398 scopus 로고    scopus 로고
    • note
    • See the Experimental Section for details regarding rate law derivation.
  • 48
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    • note
    • 2Pt" fragment.
  • 49
    • 5244341084 scopus 로고    scopus 로고
    • note
    • In all kinetic runs, the NMR tubes were heated briefly at 50 °C to dissolve the substrate. The integrity of the sample was confirmed by NMR prior to kinetic runs at 70 °C. In the case of 1,2-bis[p-(trifluoromethyl)phenyl]acetylene, approximately 50% of the alkyne was diborylated during dissolution at 50 °C.
  • 51
    • 85087581714 scopus 로고    scopus 로고
    • note
    • 1H} NMR spectra, which corresponded to the reported literature values.
  • 52
    • 0001096291 scopus 로고
    • The B-B bond in PinB-BPin measures 1.711(6) Å and is significantly longer than the B-B bond in related catecholate deriva-tives where the B-B distances are 1.68 Å: Nöth, H. Z. Naturforsch. 1984, 39b, 1463-1466.
    • (1984) Z. Naturforsch. , vol.39 B , pp. 1463-1466
    • Nöth, H.1
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    • Alkyne complexes in these systems are known to react via associative and dissociative pathways: Birk, J. P.; Halpern, J.; Pickard, A. L. Inorg. Chem. 1968, 7, 2672-2673.
    • (1968) Inorg. Chem. , vol.7 , pp. 2672-2673
    • Birk, J.P.1    Halpern, J.2    Pickard, A.L.3
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    • For olefinic protons: (a) Engman, L. J. Org. Chem. 1984, 49, 3559-3563.
    • (1984) J. Org. Chem. , vol.49 , pp. 3559-3563
    • Engman, L.1


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.