Versatile Reactions Undergone by Carbenes and Nitrenes in Noble Gas Matrices at Cryogenic Temperatures

Access this Article

Search this Article

Author(s)

Abstract

A series of phenyldiazomethanes and phenyl azides bearing proximate substituents matrix-isolated in Ar at cryogenic temperatures have been photolyzed. Products are characterized mainly by IR spectroscopy in combination with ab initio theoretical calculations. In most cases, several intermediates are produced as a result of interaction between the divalent centers and the proximate functional group; they are photo-interconvertible under these conditions. <br>Phenylcarbenes and phenylnitrenes having hydrogen donors such as CH<sub>3</sub>, OH, and NH<sub>2</sub> groups at the <i>ortho</i> position have been shown to abstract hydrogen to form <i>o</i>-quinonoid compounds. Both the carbene and nitrene undergo oxygen transfer from the nitro group at the <i>ortho</i> position to form the corresponding nitroso compounds. While phenylcarbene interacts with <i>o</i>-CO<sub>2</sub>Me group to generate the corresponding carbonyl ylide, phenylnitrene undergoes 1,4-MeO shift in its excited states to produce 5-carbonyl-6-methoxyimino-1,3-cyclohexadiene. Interesting differences in the reactivity between carbenes and nitrenes are noted; these are discussed in terms of the electronic configuration, singlet-triplet energy gap and tunneling. <br>1,3-Bis(diazo) ketones incorporated in five- and seven-membered rings are prepared and photolyzed under matrix conditions. While the seven-membered ring bis(diazo)ketone affords phenanthryne by way of 9,10-cyclopropa-phenanthren-3′-one, the five-membered analogue generates 1,2-cyclopropabenzocyclobutadien-3′-one, which does not undergo photodecarbonylation to form benzocyclobutenyne. <br>Finally, a series of bis(divalent) species conjugatively connected through aromatic rings are generated and characterized. In both <i>p</i>- and <i>o</i>-phenylene systems, there is a significant interaction between the benzene nucleus and the divalent substituents. The species are best regarded as <i>p</i>- and <i>o</i>-quinonoidal biradical structures, respectively, having a singlet ground state with a low-lying excited triplet state.

Journal

  • Bulletin of the Chemical Society of Japan

    Bulletin of the Chemical Society of Japan 71(7), 1501-1524, 1998-07-15

    The Chemical Society of Japan

References:  182

  • 1 / 2
  • <no title>

    SITZMAN E. V.

    Application of Picosecond Spectroscopy to Chemistry, 1984

    Cited by (1)

  • <no title>

    DUNKIN I. R.

    Chem. Soc. Rev. 9, 1, 1980

    Cited by (3)

  • <no title>

    SHERIDAN R. S.

    Organic Photochemistry 8, 159-248, 1987

    Cited by (2)

  • <no title>

    MAYER B.

    Low Temperature Spectrpscopy, 1971

    Cited by (1)

  • <no title>

    CRADDOCK S.

    Matrix Isolation, 1975

    Cited by (1)

  • <no title>

    HALLAN H. E.

    Apectroscopy of Trapped Species, 1973

    Cited by (1)

  • <no title>

    HEHRE W.

    Ab Initio Molecular Orbital Theory, 1986

    Cited by (1)

  • <no title>

    SCAIANO J. C.

    Kinetics and Spectroscopy of Carbenes and Biradical, 353-368, 1990

    Cited by (1)

  • <no title>

    BRINKER U. H.

    Advances in Carbene Chemistry, 1994

    Cited by (1)

  • <no title>

    REGITZ M.

    Carbene (oide), Carbine E19b, 1989

    Cited by (1)

  • <no title>

    WENTRUP C.

    Reactive Molecules, 1984

    Cited by (1)

  • <no title>

    MOSS R. A.

    Carbenes 1/2, 1975

    Cited by (1)

  • <no title>

    KRIMSE W.

    Carbene Chemistry, 1971

    Cited by (1)

  • <no title>

    SCHUSTER G. B.

    Adv. Photochem. 17, 1992

    Cited by (1)

  • <no title>

    SCRIVEN E. F. V.

    Azides and Nitrenes, Reactivity and Utility, 1984

    Cited by (5)

  • <no title>

    SCRIVEN E. F. V.

    Reactive Intermediates 2, 1-54, 1981

    Cited by (1)

  • <no title>

    IDDON B.

    Angew. Chem., Int. Ed. Engl. 18, 900, 1979

    Cited by (2)

  • <no title>

    LWOWSKI W.

    Nitrenes, 1970

    Cited by (3)

  • <no title>

    MCMAHON R. J.

    J. Am. Chem. Soc. 109, 2456, 1987

    Cited by (2)

  • <no title>

    CHAPMAN O. L.

    J. Org. Chem. 52, 1218, 1987

    Cited by (1)

  • <no title>

    CHAPMAN O. L.

    J. Am. Chem. Soc. 100, 282, 1978

    Cited by (4)

  • <no title>

    HAYES O. L.

    J. Am. Chem. Soc. 112, 5879, 1990

    Cited by (1)

  • <no title>

    CHAPMAN O. L.

    Recl. Trav. Chim. Pays-Bas 98, 334, 1979

    Cited by (1)

  • <no title>

    CHAPMAN O. L.

    J. Am. Chem. Soc. 100, 6245, 1978

    Cited by (1)

  • <no title>

    GASPAR P. P.

    Tetrahedron 41, 1479, 1985

    Cited by (1)

  • <no title>

    BROWN R. F. C.

    Pyrolytic Bethods in Organic Chemistry, 1980

    Cited by (1)

  • <no title>

    WENTRUP C.

    Reactive Intermediates 1, 263-320, 1980

    Cited by (1)

  • <no title>

    JONES W. M.

    Acc Chem. Res. 10, 353, 1979

    Cited by (1)

  • <no title>

    JONES W. M.

    Rearrangement in Ground and Excited States 1, 95-160, 1980

    Cited by (1)

  • <no title>

    TOMIOKA H.

    J. Org. Chem. 56, 4196, 1993

    Cited by (1)

  • <no title>

    TOMIOKA H.

    J. Am. Chem. Soc. 113, 8771, 1991

    Cited by (2)

  • <no title>

    AHAFFER M. W.

    J. Phys. Chem. 95, 7273, 1991

    Cited by (1)

  • <no title>

    PLATZ M. S.

    Acc. Chem. Res. 28, 487, 1995

    Cited by (3)

  • <no title>

    MCMAHON R. J.

    J. Am. Chem. Soc. 109, 683, 1987

    Cited by (2)

  • <no title>

    MORAWIETZ J.

    J. Org. Chem. 60, 6368, 1995

    Cited by (3)

  • <no title>

    TOMIOKA H.

    Chem. Lett. 1997, 399

    Cited by (1)

  • <no title>

    FELIX D.

    Org. Synth. 6, 679, 1988

    Cited by (1)

  • <no title>

    MCLNTOSH C. C.

    J. Chem. Soc., Chem. Commun. 1971, 771

    Cited by (1)

  • <no title>

    TOMIOKA H.

    Liebigs Ann. 1996, 1971

    Cited by (1)

  • <no title>

    MORAWIETZ J.

    Liebigs Ann. 1996, 2029

    Cited by (1)

  • <no title>

    TOMIOKA H.

    Pure Appl. Chem. 69, 837, 1997

    Cited by (1)

  • <no title>

    SANDER W.

    Angew. Chem. Int. Ed. Engl. 29, 344, 1990

    Cited by (7)

  • <no title>

    PLATZ M. S.

    J. Am. Chem. Soc. 101 and 102, 3398 and 1192, 1980

    Cited by (1)

  • <no title>

    PLATZ M. S.

    Tetrahedron 38, 777, 1982

    Cited by (1)

  • <no title>

    BIEWER M. C.

    J. Am. Chem. Soc. 113, 8069, 1991

    Cited by (1)

  • <no title>

    HOMBERGER G.

    J. Am. Chem. Soc. 111, 475, 1989

    Cited by (2)

  • <no title>

    KIRMSE W.

    J. Am. Chem. Soc. 114, 7590, 1992

    Cited by (2)

  • <no title>

    KIRMSE W.

    J. Am. Chem. Soc. 115, 792, 1993

    Cited by (2)

  • <no title>

    LIAS S. G.

    J. Phys. Chem. Ref. Data 17, Suppl. 1, 1988

    Cited by (12)

  • <no title>

    BERKOWITZ J.

    Acc. Chem. Res. 22, 413, 1989

    Cited by (1)

  • <no title>

    HAIDER K. W.

    Chem. Phys. Lett. 164, 443, 1989

    Cited by (1)

  • <no title>

    BAER T. A.

    J. Am. Chem. Soc. 93, 5180, 1971

    Cited by (1)

  • <no title>

    MOSS R. A.

    J. Am. Chem. Soc. 93, 954, 1971

    Cited by (1)

  • <no title>

    KIM S. J.

    J. Am. Chem. Soc. 114, 5349, 1992

    Cited by (2)

  • <no title>

    HROVAT D. A.

    J. Am. Chem. Soc. 114, 8698, 1992

    Cited by (3)

  • <no title>

    TRAVERS M. J.

    J. Am. Chem. Soc. 114, 8699, 1992

    Cited by (1)

  • <no title>

    GRILLER D.

    J. Am. Chem. Soc. 106, 198, 1984

    Cited by (1)

  • <no title>

    GRILLER D.

    Tetrahedron 41, 1525, 1985

    Cited by (1)

  • <no title>

    PLATZ M. S.

    Kinetics and Spectroscopy of Carbenes and Biradicals, 320-333, 1990

    Cited by (1)

  • <no title>

    SCHUSTER G.

    Adv. Phys. Org. Chem 22, 311, 1986

    Cited by (1)

  • <no title>

    POE R.

    J. Am. Chem. Soc. 113, 3209, 1991

    Cited by (3)

  • <no title>

    POE R.

    J. Am. Chem. Soc 114, 5054, 1992

    Cited by (3)

  • <no title>

    YOUNG M. J. T.

    J. Org. Chem. 56, 6403, 1991

    Cited by (1)

  • <no title>

    SOUNDARARAJAN N.

    J. Org. Chem. 55, 3640, 1990

    Cited by (1)

  • <no title>

    PLATZ M. S.

    Kinetics and Spectroscopy of Carbenes and Biradicals 143, 1990

    Cited by (1)

  • <no title>

    PLATZ M. S.

    Acc. Chem. Res. 21, 236, 1988

    Cited by (1)

  • <no title>

    WRIGHT B. B.

    Tetrahedron 41, 1517, 1985

    Cited by (1)

  • <no title>

    TOMIOKA H.

    Res. Chem. Intermed. 20, 605, 1994

    Cited by (1)

  • <no title>

    BELL R. P.

    The Tunnel Effect in Chemistry, 1980

    Cited by (2)

  • <no title>

    DIA L.

    J. Am. Chem. Soc. 117, 5369, 1995

    Cited by (1)

  • <no title>

    WANG P.

    Can. J. Chem. 74, 465, 1996

    Cited by (1)

  • <no title>

    OPPOLZER W.

    Comprehensive Organic Synthesis 5, 385-396, 1991

    Cited by (1)

  • <no title>

    JOHSON L. J.

    Chem. Rev. 89, 521, 1989

    Cited by (1)

  • <no title>

    MEIER H.

    Angew. Chem., Int. Ed. Engl. 26, 1046, 1987

    Cited by (1)

  • <no title>

    SCHMIDT M.

    Chem. Ber. 123, 1143, 1990

    Cited by (2)

  • <no title>

    MEIER H.

    Tetrahedron Lett. 36, 6043, 1995

    Cited by (1)

  • <no title>

    PAUL G. C.

    J. Org. Chem. 58, 5060, 1993

    Cited by (2)

  • <no title>

    GARDUER P. D.

    J. Am. Chem. Soc. 81, 5515, 1959

    Cited by (2)

  • <no title>

    JIMENEZ M. C.

    J. Org. Chem. 59, 197, 1994

    Cited by (2)

  • <no title>

    MEIER G.

    Angew. Chem., Int. Ed. Engl. 17, 121, 1978

    Cited by (1)

  • <no title>

    PFISTER-GUILLOUZO G.

    Tetrahedron Lett. 33, 5753, 1992

    Cited by (1)

  • <no title>

    SMOLINSKI G.

    J. Org. Chem. 26, 4108, 1961

    Cited by (2)

  • <no title>

    BURGESS E. M.

    J. Am. Chem. Soc. 88, 1580, 1966

    Cited by (3)

  • <no title>

    MURATA S.

    J. Am. Chem. Soc. 107, 6317, 1985

    Cited by (2)

  • <no title>

    GOLDEN A. H.

    J. Org. Chem. 61, 4460, 1996

    Cited by (2)

  • <no title>

    KUMAR A.

    J. Org. Chem. 61, 4402, 1996

    Cited by (1)

  • <no title>

    ADAM W.

    J. Am. Chem. Soc. 115, 8603, 1993

    Cited by (1)

  • <no title>

    ADAM W.

    Chem. Ber. 127, 1115, 1994

    Cited by (1)

  • <no title>

    SCAIANO J. C.

    J. Org. Chem. 54, 1612, 1989

    Cited by (5)

  • <no title>

    CASAL H. L.

    J. Org. Chem. 49, 5214, 1984

    Cited by (2)

  • <no title>

    CLARK K. B.

    J. Org. Chem. 57, 3706, 1992

    Cited by (1)

  • <no title>

    KOVACS D.

    J. Am. Chem. Soc. 118, 8144, 1996

    Cited by (1)

  • <no title>

    KIRMSE W.

    J. Am. Chem. Soc. 111, 1465, 1989

    Cited by (2)

  • <no title>

    L'ESPERANCE R. P.

    J. Am. Chem. Soc. 110, 209, 1988

    Cited by (2)

  • <no title>

    MURATA S.

    Chem. Lett. 1992, 57

    Cited by (1)

  • <no title>

    HACKER N. P.

    J. Org. Chem. 56, 5216, 1991

    Cited by (1)

  • <no title>

    DUNKIN I. R.

    J. Chem. Soc., Chem. Commun. 1991, 1178

    Cited by (2)

  • <no title>

    BOULTON A. J.

    Heterocyclic Chemistry 10, 1, 1969

    Cited by (1)

  • <no title>

    BRADLEY G. M.

    J. Phys. Chem. 79, 1953, 1975

    Cited by (1)

  • <no title>

    PONDER M.

    J. Org. Chem. 59, 6431, 1994

    Cited by (1)

  • 1 / 2

Codes

  • NII Article ID (NAID)
    10008933558
  • NII NACSIS-CAT ID (NCID)
    AA00580132
  • Text Lang
    ENG
  • Article Type
    ART
  • ISSN
    00092673
  • NDL Article ID
    4525704
  • NDL Source Classification
    ZP1(科学技術--化学・化学工業)
  • NDL Call No.
    Z53-B35
  • Data Source
    CJP  NDL  J-STAGE 
Page Top