Reactions of silane with cerium atoms:triply hydrogen-bridged Si(μ-H)_3CeH and inserted H_3SiCeH
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- 英文论文题名：Reactions of silane with cerium atoms:triply hydrogen-bridged Si(μ-H)_3CeH and inserted H_3SiCeH
- 论文作者：Peipei Shi ; Bing Xu
- 英文论文作者：Peipei Shi ; Bing Xu ; Shanghai Key Lab of Chemical Assessment and Sustainability ; Department of Chemistry ; Tongji University
- 年：2016
- 作者机构：Shanghai Key Lab of Chemical Assessment and Sustainability, Department of Chemistry,Tongji University;
- 英文论文关键词：matrix isolation FTIR ; cerium atoms ; hydrogen bridge bonds
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第四十四分会：化学动力学
- 语种：英文
- 分类号：O641.3
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第四十四分会 ; 化学动力学
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：150k
- 原文格式：D
- 会议级别：全国
摘要
Reactions of laser-ablated cerium atoms with silane in solid argon and krypton matrices have been investigated by matrix isolation FTIR and theoretical calculations. It is found that the ground state cerium atoms can react with SiH 4 to form the Si(μ-H)_3CeH and H_3SiCeH spontaneously. Firstly, one hydrogen atom of SiH_4 shifted to Ce atom, forming the mono-bridged H_2Si(μ-H)CeH. Secondly, the bridged H atom shifted to Si atom to produce the inserted H_3SiCeH. Thirdly, the H_3SiCeH formed the triply hydrogen-bridged Si(μ-H)_3CeH directly. These molecules have been identified on the basis of the SiD_4 isotopic substitutions. In addition, DFT calculations were used to predict energies, geometries, and vibrational frequencies for these new structures, showing that the triplet state of triply hydrogen-bridged Si(μ-H)_3CeH complexes are the most stable among all the isomers. In this system, Ce atom donates one electron to Si atom, which makes Si(μ-H)_3 fragment similar to monoanion, consistent with the CeH monocation. Three pairs of Si-H σ bonds donate to the virtual hybrid orbital(43.0% 6s and 52.7% 5d of Ce atom) of CeH fragment, facilitating to the formation of hydrogen bridge bonds.
Reactions of laser-ablated cerium atoms with silane in solid argon and krypton matrices have been investigated by matrix isolation FTIR and theoretical calculations. It is found that the ground state cerium atoms can react with SiH 4 to form the Si(μ-H)_3CeH and H_3SiCeH spontaneously. Firstly, one hydrogen atom of SiH_4 shifted to Ce atom, forming the mono-bridged H_2Si(μ-H)CeH. Secondly, the bridged H atom shifted to Si atom to produce the inserted H_3SiCeH. Thirdly, the H_3SiCeH formed the triply hydrogen-bridged Si(μ-H)_3CeH directly. These molecules have been identified on the basis of the SiD_4 isotopic substitutions. In addition, DFT calculations were used to predict energies, geometries, and vibrational frequencies for these new structures, showing that the triplet state of triply hydrogen-bridged Si(μ-H)_3CeH complexes are the most stable among all the isomers. In this system, Ce atom donates one electron to Si atom, which makes Si(μ-H)_3 fragment similar to monoanion, consistent with the CeH monocation. Three pairs of Si-H σ bonds donate to the virtual hybrid orbital(43.0% 6s and 52.7% 5d of Ce atom) of CeH fragment, facilitating to the formation of hydrogen bridge bonds.
Reactions of laser-ablated cerium atoms with silane in solid argon and krypton matrices have been investigated by matrix isolation FTIR and theoretical calculations. It is found that the ground state cerium atoms can react with SiH 4 to form the Si(μ-H)_3CeH and H_3SiCeH spontaneously. Firstly, one hydrogen atom of SiH_4 shifted to Ce atom, forming the mono-bridged H_2Si(μ-H)CeH. Secondly, the bridged H atom shifted to Si atom to produce the inserted H_3SiCeH. Thirdly, the H_3SiCeH formed the triply hydrogen-bridged Si(μ-H)_3CeH directly. These molecules have been identified on the basis of the SiD_4 isotopic substitutions. In addition, DFT calculations were used to predict energies, geometries, and vibrational frequencies for these new structures, showing that the triplet state of triply hydrogen-bridged Si(μ-H)_3CeH complexes are the most stable among all the isomers. In this system, Ce atom donates one electron to Si atom, which makes Si(μ-H)_3 fragment similar to monoanion, consistent with the CeH monocation. Three pairs of Si-H σ bonds donate to the virtual hybrid orbital(43.0% 6s and 52.7% 5d of Ce atom) of CeH fragment, facilitating to the formation of hydrogen bridge bonds.
引文
[1]Han-Shi Hu,Fan Wei,Xuefeng Wang,Lester Andrews,and Jun Li.J.Am.Chem.Soc.2014,136,1427-1437.
[2]Xuefeng Wang,Lester Andrews.J.Am.Chem.Soc.2008,130,6766–6773.
[3]M.Lein,A.Krapp,G.Frenking,J.Am.Chem.Soc.2005,127,6290-6299.
[2]Xuefeng Wang,Lester Andrews.J.Am.Chem.Soc.2008,130,6766–6773.
[3]M.Lein,A.Krapp,G.Frenking,J.Am.Chem.Soc.2005,127,6290-6299.