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  • 1
    Electronic Resource
    Electronic Resource
    Organische Synthesen mit übergangsmetall-Komplexen, 51. 1-Metalla-1,3,5-triene und 1-Metalla-1,3-dien-5-ine von Chrom und Wolfram durch Insertion von Alkinen in M=C- bzw. C=C-Bindungen von 1-Metalla-1,3-dienen bzw. 1-Metalla-1-en-2-inen (1991)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1229-1236 
    Details
    ISSN: 0009-2940
    Keywords: Carbene complexes of chromium and tungsten ; 1-Metalla-1,3,5-trienes ; 1-Metalla-1,3-dien-5-ynes ; Insertion of alkynes into M=C and C=C bonds ; [2 + 2] Cycloaddition reactions of carbene complexes and alkynes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Organic Syntheses via Transition Metal Complexes, 51. - 1-Metalla-1,3,5-trienes and 1-Metalla-1,3-dien-5-ynes of Chromium and Tungsten by Insertion of Alkynes into M=C and C=C Bonds of 1-Metalla-1,3-dienes and 1-Metalla-1-en-3-ynes, respectively1-Metalla-1,3,5-trienes LnM=C(NEt2)-C(Me)—C(OEt)-CH=CHPh (3,4) and LnM=C(OEt)- CH=C(NEt2) - C(Me)=CHPh [5, LnM=Cr(CO)5 (a), W(CO)5 (b)] are obtained for the first time from the corresponding 1-metalla-1,3-dienes LnM=C(OEt) - CH=CHPh (1a, b) under very mild conditions by the insertion of the electron-rich alkyne Et2N-C ≡ C - Me (2) into the M=C and the C=C bonds, respectively, of 1. The chelate complex (6b) and the cyclobutenyl carbene complex 7b are isolated as minor side products. 1-Metalla-1,3-dien-5-ynes LnM=C(NEt2) - C(Me)=C(OEt) - C ≡ CPh [9, 10, LnM=Cr(CO)5 (a), W(CO)5 (b)] are formed with high regio- and stereoselectivity on insertion of 2 into the M=C bonds of 1-metalla-1-en-3-ynes 8. X-ray data are given for the tungsten complex 3b.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19911240541
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  • 2
    Electronic Resource
    Electronic Resource
    Reaktive E = C(p - p)π-Systeme, XXXI Erste Vertreter aminosubstituierter 1,2,4-Diazaphosphole (1992)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 411-414 
    Details
    ISSN: 0009-2940
    Keywords: Phosphaalkyne, amino- ; [3 + 2] Cycloaddition ; 1,2,4-Diazaphospholes ; 1,2,3-Diazaphospholes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactive E = C(p - p)π Systems, XXXII[1].  -  First Representatives of Amino-Substituted 1,2,4-Diazaphospholes(Diisopropylamino)phosphaethyne iPr2N - C≡P reacts at 20° C in a [3 + 2] cycloaddition with (trifluoromethyl)diazomethane (2a) or methyl diazoacetate (2b) to yield a mixture of the corresponding regioisomers 1H-1,2,4-diazaphospholes (5a or 5b) and 1H-1,2,3-diazaphospholes (6a or 6b) in quantitative yields (isomer ratio: 5a/6a = 2:1; 5b/6b = 4:1). X-ray diffraction studies on 5a and 5b indicate a delicate charge balance in the bonding system of 1H-1,2,4,σ2-diazaphospholes under the influence of the exocyclic push/pull substituents iPr2N and CF3 or CO2Me, respectively.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19921250219
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  • 3
    Electronic Resource
    Electronic Resource
    Organic Syntheses via Transition Metal Complexes, 74[1] Novel Phosphonium Allenide and 2-Phosphanylethenyl Carbene Chromium and Tungsten Complexes (1994)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 2475-2482 
    Details
    ISSN: 0009-2940
    Keywords: Vinylcarbene complexes ; Chromium complexes ; Tungsten complexes ; Phosphorus ylide complexes ; Alkynylcarbene complexes ; Allene complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Alkynylcarbene complexes (CO)5M≡C(OEt)-C≡C—R 1 (M = Cr, W; R = Ph, tBu, SiMe3) readily add tertiary phosphanes PPhR2′ 4 (R′ = Ph, Me) to form stable zwitterionic phosphonium allenide complexes (CO)5M--C(OEt) = C≡C(R)-P+PhR2′ 5. Complex 5a (M = Cr, R = R′ = Ph) was characterized by X-ray diffraction. The addition of secondary phosphanes PHR2 6 to 1 affords red (2-phosphanyl ethenyl)-carbene complexes (CO)5M≡C(OEt)-CH≡C(R)-PR2 (E)-8 (R = tBu, cC6H11, Ph) in 34-89% isolated yields. Dinuclear complexes (CO)5M≡C(OEt)-CH≡C(R)-P(R2)M(CO)5 (E)-9 are obtained as byproducts. Compounds (E)-8b (M = Cr, R = cC6H11) and (E)-9i (M = Cr, R = Ph) were characterized by X-ray analyses.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19941271218
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