Conversion from Cyclic to Chain Structure in Boron Carbonyl Clusters:A Study of Infrared Spectroscopy of B_3(CO)_n~+ n=3-6
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- 英文论文题名：Conversion from Cyclic to Chain Structure in Boron Carbonyl Clusters:A Study of Infrared Spectroscopy of B_3(CO)_n~+ n=3-6
- 论文作者：Jiaye Jin ; Guanjun Wang ; Mingfei Zhou
- 英文论文作者：Jiaye Jin ; Guanjun Wang ; Mingfei Zhou ; Department of Chemistry ; Fudan University
- 年：2016
- 作者机构：Department of Chemistry, Fudan University;
- 英文论文关键词：Boron Carbonyl Clusters ; Infrared Photodissociation Spectroscopy ; Theoretical Calculations ; Ligand contributions ; B_3
- 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：O627.31
- 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：179k
- 原文格式：D
- 会议级别：全国
摘要
Boron is an interesting element with unusual polymorphism.B_3 is the smallest cluster in the series of pure boron clusters,which plays an important role for maintaining the 3c-2e bonds in planar and fullerene structure.Recently studies on B_3 compounds all show great stability with 2πaromaticity[1-3].Here,we report a study of infrared photodissociation spectroscopy for the B_3(CO)n~+(n=3~6)clusters in the carbonyl stretching frequency region.The clusters were generated via a laser vaporization ion source in a pulse molecule beam in gas phase;and Density functional theory was carried out in the comparison between the simulated results and the experimental spectra.The B_3(CO)_3~+has a D_(3h)symmetry with a Huckelπaromatic B_3 ring~([1]),whereas the B_3(CO)_4~+is characterized to have a D_(2d)structure with a linear Boron skeleton.The B_3(CO)_5~+is also determined to have a chain Boron framework with C_(2v)symmetry.The B_3(CO)_6~+takes B_3(CO)_5~+as the core with a tagging carbonyl ligand.We found,as the increase of the ligand number around the B_3 unit,repulsion energies between ligands rise.And thus,the boron frameworks are more like to form chain structures rather than the ring-like ones.The result provides a fundamental understanding of ligand contributions on the B_3 structure in the boron clusters.
Boron is an interesting element with unusual polymorphism.B_3 is the smallest cluster in the series of pure boron clusters,which plays an important role for maintaining the 3c-2e bonds in planar and fullerene structure.Recently studies on B_3 compounds all show great stability with 2π aromaticity[1-3].Here,we report a study of infrared photodissociation spectroscopy for the B_3(CO)_n~+(n=3~6) clusters in the carbonyl stretching frequency region.The clusters were generated via a laser vaporization ion source in a pulse molecule beam in gas phase;and Density functional theory was carried out in the comparison between the simulated results and the experimental spectra.The B_3(CO)_3~+ has a D_(3h) symmetry with a Huckel π aromatic B_3 ring,whereas the B_3(CO)_4~+ is characterized to have a D_(2d) structure with a linear Boron skeleton.The B_3(CO)_5~+ is also determined to have a chain Boron framework with C_(2v) symmetry.The B_3(CO)_6~+ takes B_3(CO)_5~+ as the core with a tagging carbonyl ligand.We found,as the increase of the ligand number around the B_3 unit,repulsion energies between ligands rise.And thus,the boron frameworks are more like to form chain structures rather than the ring-like ones.The result provides a fundamental understanding of ligand contributions on the B_3 structure in the boron clusters.
Boron is an interesting element with unusual polymorphism.B_3 is the smallest cluster in the series of pure boron clusters,which plays an important role for maintaining the 3c-2e bonds in planar and fullerene structure.Recently studies on B_3 compounds all show great stability with 2π aromaticity[1-3].Here,we report a study of infrared photodissociation spectroscopy for the B_3(CO)_n~+(n=3~6) clusters in the carbonyl stretching frequency region.The clusters were generated via a laser vaporization ion source in a pulse molecule beam in gas phase;and Density functional theory was carried out in the comparison between the simulated results and the experimental spectra.The B_3(CO)_3~+ has a D_(3h) symmetry with a Huckel π aromatic B_3 ring,whereas the B_3(CO)_4~+ is characterized to have a D_(2d) structure with a linear Boron skeleton.The B_3(CO)_5~+ is also determined to have a chain Boron framework with C_(2v) symmetry.The B_3(CO)_6~+ takes B_3(CO)_5~+ as the core with a tagging carbonyl ligand.We found,as the increase of the ligand number around the B_3 unit,repulsion energies between ligands rise.And thus,the boron frameworks are more like to form chain structures rather than the ring-like ones.The result provides a fundamental understanding of ligand contributions on the B_3 structure in the boron clusters.
引文
[1]Jin,J.Y.;Wang,G.J.;Zhou,M.F.;Andrada,D.M.;Hermann,M.;Frenking,G.,.Angew.Chem.-Int.Edit.2016,55(6),2078-2082.
[2]Kupfer,T.;Braunschweig,H.;Radacki,K.,The Triboracyclopropenyl Dianion:Angew.Chem.-Int.Edit.2015,54(50),15084-15088.
[3]Zhai,H.J.;Wang,L.S.;Alexandrova,A.N.;Boldyrev,A.I.,Journal of Physical Chemistry A2003,107(44),9319-9328.
[2]Kupfer,T.;Braunschweig,H.;Radacki,K.,The Triboracyclopropenyl Dianion:Angew.Chem.-Int.Edit.2015,54(50),15084-15088.
[3]Zhai,H.J.;Wang,L.S.;Alexandrova,A.N.;Boldyrev,A.I.,Journal of Physical Chemistry A2003,107(44),9319-9328.