The Syntheses of R<SUB>3</SUB>Sn–Mn(CO)<SUB>5−<I>n</I></SUB>L<I><SUB>n</SUB></I>(<I>n</I>=0 or 1) Compounds and Their <SUP>119</SUP>Sn-Mössbauer and <SUP>1</SUP>H-NMR Studies
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概要
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Seven new compounds with the Sn-Mn bond have been prepared by carbonyl displacement with a weaker π-accepting ligand, L (L=P(C<SUB>6</SUB>H<SUB>5</SUB>)<SUB>3</SUB>, As(C<SUB>6</SUB>H<SUB>5</SUB>)<SUB>3</SUB>, Sb(C<SUB>6</SUB>H<SUB>5</SUB>)<SUB>3</SUB> for R<SUB>3</SUB>Sn–Mn(CO)<SUB>5</SUB>) or by reaction of the anion [Mn(CO)<SUB>5</SUB>]<SUP>−</SUP> or [Mn(CO)<SUB>4</SUB>P(C<SUB>6</SUB>H<SUB>5</SUB>)<SUB>3</SUB>]<SUP>−</SUP> with R<SUB>3</SUB>SnX (R=C<SUB>2</SUB>H<SUB>5</SUB>, <I>n</I>-C<SUB>3</SUB>H<SUB>7</SUB>, <I>n</I>-C<SUB>4</SUB>H<SUB>9</SUB>). A <I>trans</I> configuration is deduced for the mono-substituted compounds, R<SUB>3</SUB>Sn–Mn(CO)<SUB>4</SUB>L, on the basis of the infrared spectra in the <I>v</I>(CO) region. The <SUP>119</SUP>Sn-Mössbauer and IR spectra are measured for sixteen compounds of the R<SUB>3</SUB>Sn–Mn(CO)<SUB>5−<I>n</I></SUB>L<I><SUB>n</SUB></I> type (R=CH<SUB>3</SUB>, C<SUB>2</SUB>H<SUB>5</SUB>, <I>n</I>-C<SUB>3</SUB>H<SUB>7</SUB>, <I>n</I>-C<SUB>4</SUB>H<SUB>9</SUB>, Cl, Br, I; L=P(C<SUB>6</SUB>H<SUB>5</SUB>)<SUB>3</SUB>, As(C<SUB>6</SUB>H<SUB>5</SUB>)<SUB>3</SUB>, Sb(C<SUB>6</SUB>H<SUB>5</SUB>)<SUB>3</SUB>; <I>n</I>=0 or 1). Both the Mössbauer isomer shift and the quadrupole splitting increase with an increase in the length of the alkyl chain attached to the tin atom. The replacement of CO on the manganese atom with the weaker π-accepting ligand, L, has a significant effect on the isomer shift and quadrupole splitting of the tin atom through the σ- and π-interaction between the tin and manganese atoms. An interpretation of the change in the chemical shift of the terminal methyl protons is also given for alkyl derivatives.
- 公益社団法人 日本化学会の論文
著者
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Onaka Satoru
Department Of Chemistry Nagoya Institute Of Technology
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Sano Hirotoshi
Deparment of Chemistry, Faculty of Science, Tokyo Metropolitan University
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