Addition of N-aryl imines to alkyne(pentacarbonyl)chromium and tungsten : a novel route to alkenyl(amino)carbene complexes

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JOM-00-599-288.pdf
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2000
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Abd-Elzaher, Mokhles M.
Froneck, Thomas
Roth, Gerhard
Gvozdev, Valentin
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Photolysis of [M(CO)6] in CH2Cl2 gives [(CO)5M(CH2Cl2)] (M=Cr, W). Replacement of CH2Cl2 by arylacetylene, HC=CC6H4R-p (R=Me, H, Br), produces the thermolabile arylacetylene complexes [(CO)5M(HC¡ÔCC6H4R-p)]. Addition of N-phenyl benzylideneimines, PhN=C(C6H4R'-p)H (R'=Me, H, Cl), to solutions of these alkyne complexes affords alkenyl( amino)carbene complexes, [(CO)5M=C(NPhH)C(C6H4R-p)=C(C6H4R'-p)H], and 2-azetidin-1-ylidene complexes, [(CO)5M=C-NPh-C(C6H4R'-p)H-C(C6H4R-p)H]. The formation of the alkenyl(amino)carbene complexes is favored. The ratio alkenyl(amino)carbene:2-azetidin-1-ylidene complex is 2.5¨C3 for M=W and 6.5¨C8 for M=Cr. Both types of complexes are obtained as mixtures of isomers. The 2-azetidin-1-ylidene complexes are very likely formed by cycloaddition of the imines to the C=C bond of vinylidene complexes resulting from tautomerization of the alkyne complexes. The cycloaddition is highly stereoselective. Predominantly, the syn isomer is obtained (syn/anti>9). In contrast, the alkenyl(amino)carbene complexes are presumably derived from the alkyne complexes via cycloaddition of the imines to the coordinated alkyne and subsequent 1,2-hydrogen shift and ring opening. Preferentially, the E isomers (where both aryl substituents are cis with respect to the C=C bond) are produced. The structure of the major isomer of the alkenyl(amino)carbene complex [(CO)5W=C(NPhH)C(C6H4Me-p) =C(Ph)H] has been established by X-ray structural analysis.

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540 Chemie
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N-aryl imines, Alkyne(pentacarbonyl)chromium, Alkyne(pentacarbonyl)tungsten
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ISO 690ABD-ELZAHER, Mokhles M., Thomas FRONECK, Gerhard ROTH, Valentin GVOZDEV, Helmut FISCHER, 2000. Addition of N-aryl imines to alkyne(pentacarbonyl)chromium and tungsten : a novel route to alkenyl(amino)carbene complexes. In: Journal of Organometallic Chemistry. 2000, 599(2), pp. 288-297. ISSN 0022-328X. Available under: doi: 10.1016/S0022-328X(00)00010-3
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@article{AbdElzaher2000Addit-9914,
  year={2000},
  doi={10.1016/S0022-328X(00)00010-3},
  title={Addition of N-aryl imines to alkyne(pentacarbonyl)chromium and tungsten : a novel route to alkenyl(amino)carbene complexes},
  number={2},
  volume={599},
  issn={0022-328X},
  journal={Journal of Organometallic Chemistry},
  pages={288--297},
  author={Abd-Elzaher, Mokhles M. and Froneck, Thomas and Roth, Gerhard and Gvozdev, Valentin and Fischer, Helmut}
}
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    <dcterms:abstract xml:lang="eng">Photolysis of [M(CO)6] in CH2Cl2 gives [(CO)5M(CH2Cl2)] (M=Cr, W). Replacement of CH2Cl2 by arylacetylene, HC=CC6H4R-p (R=Me, H, Br), produces the thermolabile arylacetylene complexes [(CO)5M(HC¡ÔCC6H4R-p)]. Addition of N-phenyl benzylideneimines, PhN=C(C6H4R'-p)H (R'=Me, H, Cl), to solutions of these alkyne complexes affords alkenyl( amino)carbene complexes, [(CO)5M=C(NPhH)C(C6H4R-p)=C(C6H4R'-p)H], and 2-azetidin-1-ylidene complexes, [(CO)5M=C-NPh-C(C6H4R'-p)H-C(C6H4R-p)H]. The formation of the alkenyl(amino)carbene complexes is favored. The ratio alkenyl(amino)carbene:2-azetidin-1-ylidene complex is 2.5¨C3 for M=W and 6.5¨C8 for M=Cr. Both types of complexes are obtained as mixtures of isomers. The 2-azetidin-1-ylidene complexes are very likely formed by cycloaddition of the imines to the C=C bond of vinylidene complexes resulting from tautomerization of the alkyne complexes. The cycloaddition is highly stereoselective. Predominantly, the syn isomer is obtained (syn/anti&gt;9). In contrast, the alkenyl(amino)carbene complexes are presumably derived from the alkyne complexes via cycloaddition of the imines to the coordinated alkyne and subsequent 1,2-hydrogen shift and ring opening. Preferentially, the E isomers (where both aryl substituents are cis with respect to the C=C bond) are produced. The structure of the major isomer of the alkenyl(amino)carbene complex [(CO)5W=C(NPhH)C(C6H4Me-p) =C(Ph)H] has been established by X-ray structural analysis.</dcterms:abstract>
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