NMR studies on zerovalent metal .PI.-complexes of dibenzylideneacetone. I. Ligand conformation and bonding in the binuclear palladium complex.
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概要
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To elucidate the ligand conformation and the metal–olefin bonding nature in the binuclear palladium complex of dibenzylideneacetone, Pd<SUB>2</SUB>[(C<SUB>6</SUB>H<SUB>5</SUB>CH=CH)<SUB>2</SUB>CO]<SUB>3</SUB>, <SUP>1</SUP>H NMR studies have been performed on the deuteriated complexes Pd<SUB>2</SUB>[(C<SUB>6</SUB>D<SUB>5</SUB>CH=CH)<SUB>2</SUB>CO]<SUB>3</SUB>, Pd<SUB>2</SUB>[(C<SUB>6</SUB>D<SUB>5</SUB>CD=CH)<SUB>2</SUB>CO]<SUB>3</SUB>, and Pd<SUB>2</SUB>[(C<SUB>6</SUB>D<SUB>5</SUB>CH=CD)<SUB>2</SUB>CO]<SUB>3</SUB>. Examination of the spectra has revealed that the three dibenzylideneacetone ligands which triply bridge the two Pd atoms are all in the <I>s</I>-<I>cis</I>,<I>trans</I> conformation. The most probable bonding scheme of the three ligands to the two Pd atoms is as follows: one Pd atom is ligated by one <I>s</I>-<I>trans</I> and two <I>s</I>-<I>cis</I> olefinic moieties and hence the other by one <I>s</I>-<I>cis</I> and two <I>s</I>-<I>trans</I> to yield a metal–olefin bonding stronger in the former combination than in the latter. A linear correlation between the couplings and the mean chemical shifts of the <I>trans</I> olefinic protons suggests a dominant role of metal between the couplings and the mean chemical shifts of the <I>trans</I> olefinic protons suggests a dominant role of metal to olefin π-back donation in differentiating the olefinic moieties in their bonding strength to the metal atoms and in retaining the characteristic rigid structure of the complex.
- 公益社団法人 日本化学会の論文
著者
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Yamada Koh-ichi
Faculty Of Pharmaceutical Sciences Josai University
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Kawazura Hiroshi
Faculty Of Pharmaceutical Sciences Josai University
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Tanaka Hisao
Faculty Of Pharmaceutical Sciences Josai University
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Ishii Yoshio
Department Of Information Systems Science Faculty Of Engineering Soka University
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Takahashi Toshio
Department Of Applied Physics Faculty Of Engineering University Of Tokyo
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Takahashi Toshio
Department of synthetic Chemistry, Faculty of Engineering, Nagoya University
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