Kinetic Studies of Oxygen Atom Transfer Reactions between Various cis-Dioxobis(dithiocarbamato)molybdenum(VI) Complexes and Triphenylphosphine.

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概要

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• The kinetics of the oxygen atom transfer reactions between <I>cis</I>-[MoO<SUB>2</SUB>(R<SUB>2</SUB>dtc)<SUB>2</SUB>] [R=CH<SUB>3</SUB>, C<SUB>2</SUB>H<SUB>5</SUB>, <I>i</I>-C<SUB>3</SUB>H<SUB>7</SUB>, <I>i</I>-C<SUB>4</SUB>H<SUB>9</SUB>, C<SUB>6</SUB>H<SUB>5</SUB>CH<SUB>2</SUB> (Bz), C<SUB>6</SUB>H<SUB>5</SUB> (Ph)] and PPh<SUB>3</SUB> (coupled reactions 1 and 2) have been investigated.<BR>[MoO<SUB>2</SUB>(R<SUB>2</SUB>dtc)<SUB>2</SUB>]+PPh<SUB>3</SUB>\xrightarrow<I>k</I><SUB>1</SUB>[MoO(R<SUB>2</SUB>dtc)<SUB>2</SUB>]+OPPh<SUB>3</SUB> (1)<BR>[MoO<SUB>2</SUB>(R<SUB>2</SUB>dtc)<SUB>2</SUB>]+MoO(R<SUB>2</SUB>dtc)<SUB>2</SUB>]\overset<I>K</I><SUB>d</SUB>\rightleftharpoons[Mo<SUB>2</SUB>O<SUB>3</SUB>(R<SUB>2</SUB>dtc)<SUB>4</SUB>] (2)<BR>The rate constants (<I>k</I><SUB>1</SUB>) of oxygen atom transfer reaction 1 correlate with the formal potentials of [MoO<SUB>2</SUB>(R<SUB>2</SUB>dtc)<SUB>2</SUB>]<SUP>0⁄−1</SUP> except for R=Bz and Ph. The equilibrium constant values (<I>K</I><SUB>d</SUB>) of dimerization reaction 2 decrease with increase of the electron-donating ability of the substituents on the dithiocarbamate ligands.

• 公益社団法人 日本化学会の論文

著者

• Ogino Hiroshi

  Department Of Chemistry Faculty Of Science Tohoku University

• Kato Yoshikiyo

  Department Of Chemistry Faculty Of General Education Yamagata University

• Iwase Akio

  Department of Chemistry, Faculty of Science, Yamagata University

• Unoura Kei

  Department of Chemistry, Faculty of Science, Yamagata University

• Unoura Kei

  Department of Chemistry, Faculty of Science, Tohoku University

• Abe Katsuaki

  Department of Chemistry, Faculty of Science, Yamagata University

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