遷移金属錯体によるσ結合活性化とその関連反応に関する理論的研究

• 榊 茂好

  熊本大学工学部物質生命化学科

書誌事項

タイトル別名

• .SIGMA.-Bond Activation by Transition Metal Complexes and Its Analogous Reactions. A Theoretical Study.
• センイ キンゾク サクタイ ニ ヨル シグマ ケツゴウ カッセイカ ト ソノ カンレン ハンノウ ニ カンスル リロンテキ ケンキュウ

抄録

Though C-H σ-bond activation of methane by platinum (0) and palladium (0) complexes, M- (PH₃) ₂ (M=Pd or Pt), is significantly endothermic and requires a considerably large activation barrier, a platinum (0) chelate-phosphine complex can perform the C-H σ-bond activation. This is interpreted in terms of distortion energy and d orbital energy. However, a palladium (0) complex cannot perform it even with a chelate-phosphine. An electron-withdrawing CN group on the sp³ C atom also accelerates the C-H σ-bond activation, because the CN group stabilizes the transition state through a charge-transfer interaction between Pd d and CN π^* orbitals and strengthens the palladium-alkyl bond. As a result, the palladium (0) chelate-phsophine complex can perform the C-H σ-bond activation of dicyanomethane. On the other hand, a palladium (II) carboxylate complex easily perfomrs the C-H σ-bond activation of methane and benzene through heterolytic C-H bond fission. This bond fission is assisted by conversion of the carboxylate ligand to carboxylic acid.

収録刊行物

• 有機合成化学協会誌

  有機合成化学協会誌 58 (12), 1189-1201, 2000

  公益社団法人 有機合成化学協会

キーワード

• homolytic σ bond activation
• hetrolytic σ bond activation
• theoretical investigation
• platinum (0)
• palladium (0)
• chelate-phosphine
• palladium (II)
• π-allyl palladium (II)

詳細情報

• CRID: 1390001205278635776
• NII論文ID: 10008824653
• NII書誌ID: AN0024521X
• DOI: 10.5059/yukigoseikyokaishi.58.1189
• ISSN: 18836526
• ISSN: 00379980
• NDL書誌ID: 5594728
• Web Site: https://ndlsearch.ndl.go.jp/books/R000000004-I5594728
• 本文言語コード: ja
• データソース種別:
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  • NDL
  • Crossref
  • CiNii Articles
• 抄録ライセンスフラグ: 使用不可