C−C Bond Cleavage of Acetonitrile by a Carbonyl Iron Complex with a Silyl Ligand
C−C Bond Cleavage of Acetonitrile by a Carbonyl Iron Complex with a Silyl Ligand
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DOI：
10.1021/om0208319
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发表时间：
2004
期刊：
影响因子：
2.8
通讯作者：
H. Nakazawa;Takafumi Kawasaki;K. Miyoshi;C. Suresh;N. Koga
中科院分区：
文献类型：
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作者：
H. Nakazawa;Takafumi Kawasaki;K. Miyoshi;C. Suresh;N. Koga
甲硅烷基铁配合物 Cp(CO)2Fe(SiMe3) (1) 在乙腈中，在 P(NMeCH2)2(OMe) (L) 存在下发生光反应，生成 Cp(CO)LFeMe (2)、CpL2FeMe (3) 和 CpL2Fe(CN) (4)，表明乙腈的碳碳键发生断裂。这些CC键断裂产物也是在L存在下，1与1当量MeCN在THF中的光反应中获得的。与CD3CN的反应表明产物中铁上的甲基源自乙腈。 Cp(CO)2Fe(ER3) (ER3 = CH3, GeMe3, SnMe3) 的相应反应生成了 CO/L 交换络合物 Cp(CO)LFe(ER3)，表明铁上的甲硅烷基配体对于乙腈的 C−C 键断裂是必不可少的。使用混合 DFT-B3LYP 方法对 C−C 键断裂进行了理论研究。乙腈直接 C−C 键氧化加成到 16e 物质 Cp(CO)Fe(SiMe3) 上，预计在光反应条件下很容易从 1 形成，具有 52.7 kcal/mol 的非常高的活化势垒，表明...
The photoreaction of a silyl iron complex Cp(CO)2Fe(SiMe3) (1) in acetonitrile in the presence of P(NMeCH2)2(OMe) (L) yielded Cp(CO)LFeMe (2), CpL2FeMe (3), and CpL2Fe(CN) (4), showing that carbon−carbon bond cleavage of acetonitrile was achieved. These C−C bond cleavage products were also obtained in the photoreaction of 1 with 1 equiv of MeCN in THF in the presence of L. The reaction with CD3CN showed that the methyl group on the iron in the products is derived from acetonitrile. The corresponding reaction of Cp(CO)2Fe(ER3) (ER3 = CH3, GeMe3, SnMe3) generated a CO/L exchange complex, Cp(CO)LFe(ER3), showing that a silyl ligand on the iron is indispensable for the C−C bond cleavage of acetonitrile. Theoretical studies on the C−C bond cleavage were performed using the hybrid DFT-B3LYP method. The direct C−C bond oxidative addition of acetonitrile to the 16e species Cp(CO)Fe(SiMe3) expected to readily form from 1 in the photoreaction conditions has a very high activation barrier of 52.7 kcal/mol, suggestin...