Synthesis and Reactions of Titanoxycarbene-Metal Carbonyl Complexes.
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概要
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A family of titanoxycarbene–metal carbonyl complexes of formula Cp<SUP>*</SUP><SUB>2</SUB>TiOC(=M<I>L<SUB>n</SUB></I>)CH<SUB>2</SUB>CH<SUB>2</SUB> (<B>3</B>), where Cp<SUP>*</SUP>=η<SUP>5</SUP>-C<SUB>5</SUB>Me<SUB>5</SUB> and M<I>L<SUB>n</SUB></I>=Cr(CO)<SUB>5</SUB>, Mo(CO)<SUB>5</SUB>, W(CO)<SUB>5</SUB>, Mn<SUB>2</SUB>(CO)<SUB>9</SUB>, and Re<SUB>2</SUB>(CO)<SUB>9</SUB>, has been prepared by the treatment of titanocene-ethylene complex <B>1</B> with metal carbonyls of group 6 and 7. Complex <B>3b</B> crystallizes in space group <I>P</I>2⁄<I>a</I> (<I>Z</I>=8) with cell constants <I>a</I>=30.401(1), <I>b</I>=9.251(1), <I>c</I>=27.561(5) Å, β=105.73(1)°, and <I>V</I>=7460(2) Å<SUP>3</SUP> (data taken at −40 °C, 6715 reflections, <I>R</I>=0.069). Two independent molecules of <B>3b</B> in crystal make an enantiomorphic pair. A notable feature of the structure is the long distance of Ti–O bond coupled with the short distance of C(2)–O bond, which is characterized by a large contribution of zwitterionic canonical form <B>7</B>. Thermal decomposition of <B>3</B> affords ethylene and the corresponding metal carbonyls, indicating that the C(carbenic)–C(3) bond fission occurred selectively, which is rather unusual for conventional Fischer-type carbene complexes. Complexes <B>3</B> react rapidly with atmospheric pressure of carbon monoxide below −30°C to produce cyclic acyltitanium complexes <B>12</B>. The reverse reactions occur even below −30°C upon replacement of carbon monoxide by argon. Complex <B>3b</B> also reacts with <I>t</I>-butyl isocyanide with a cleavage of the Ti–O bond to give 1 : 2 adduct <B>17</B>, whose molecular structure has been elucidated by X-ray crystallography [<I>P</I>2<SUB>1</SUB>⁄<I>n</I> with cell constants <I>a</I>=14.964(2), <I>b</I>=26.207(4), <I>c</I>=14.719(3) Å, β=100.30(1)°, and <I>V</I>=5679(2) Å<SUP>3</SUP> (measured at −120°C, 5311 reflections, <I>R</I>=0.068)], revealing that it has a novel zwitterionic structure possessing (η<SUP>2</SUP>-imidoyl)titanium cation and anionic acyldirhenium carbonyl moieties linked by an ethylene bridge. The controlled experiments show that complex <B>16</B> in which acyl ligand is trans to the Re–Re bond is the precursor of complex <B>17</B>. Complex <B>18</B>, a tungsten analogue of <B>17</B>, has also been prepared. Reactions of <B>3b</B> and <B>3e</B> with acetylenes are also described.
- 公益社団法人 日本化学会の論文
著者
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Mashima Kazushi
Department Of Chemistry Graduate School Of Engineering Science Osaka University
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Jyodoi Kouki
Department Of Applied Chemistry Faculty Of Engineering Kumamoto University
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Ohyoshi Akira
Department Of Applied Chemistry Faculty Of Engineering Kumamoto University
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TAKAYA Hidemasa
Department of Industrial Chemistry, Faculty of Engineering, Kyoto University
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Ohyoshi Akira
Department of Synthetic Chemistry, Faculty of Engineering, Kumamoto University
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Takaya Hidemasa
Department of Chemistry, Nagoya University
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