Chemical reactivities of coordinatively unsaturated hydridotris(phosphonite)-cobalt(I) species photogenerated towards allylic and related compounds.
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概要
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Pyrex-filtered photoirradiation with a high-pressure Hg lamp was performed for a thermally inert hydridocobalt(I) CoH[PPh(OEt)<SUB>2</SUB>]<SUB>4</SUB> in the presence of some allylic compounds. Allyl benzoate and allyl phenyl ether showed the cleavage of allylic-O bonds to give propene in a stoichiometric quantity to the complex charged. Photoassisted catalytic double-bond migration occurred for <I>N</I>-allylacetamide, <I>N</I>,<I>N</I>-diethylallylamine, and allylbenzene to afford the respective (<I>E</I>)- and (<I>Z</I>)-1-propenyl derivatives with kinetically controlled <I>E</I>, <I>Z</I> compositions, and the fractions of <I>Z</I> isomers at the initial stage of the reaction proceeding were near 79, 30, and 20%, respectively. Laser flash photolysis study revealed that the double-bond migration was initiated by the coordination of the substrates through C=C double bond rather than nitrogen or oxygen donor-atom to the coordinatively unsaturated species "CoH[PPh(OEt)<SUB>2</SUB>]<SUB>3</SUB>" photogenerated.
- 公益社団法人 日本化学会の論文
著者
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Hiraki Katsuma
Department Of Applied Chemistry Faculty Of Engineering Nagasaki University
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Onishi Masayoshi
Department Of Applied Chemistry Faculty Of Engineering Nagasaki University
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Oishi Shigero
Sagami Chemical Research Center
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Sakaguchi Mitoshi
Department of Industrial Chemistry, Faculty of Engineering, Nagasaki University
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Takaki Isato
Department of Industrial Chemistry, Faculty of Engineering, Nagasaki University
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