Infrared Photodissociation Spectroscopy and Density Functional Theory Study of Heteronuclear Transition Metal Carbonyl Cations in Gas Phase
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- 英文论文题名：Infrared Photodissociation Spectroscopy and Density Functional Theory Study of Heteronuclear Transition Metal Carbonyl Cations in Gas Phase
- 论文作者：Hui Qu ; Fanchen Kong ; Guanjun Wang ; Mingfei Zhou
- 英文论文作者：Hui Qu ; Fanchen Kong ; Guanjun Wang ; Mingfei Zhou ; Department of Chemistry ; Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials ; Fudan University
- 年：2016
- 作者机构：Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Fudan University;
- 英文论文关键词：metal-metal bond ; infrared photodissociation spectroscopy ; density functional theory ; transition metal carbonyl
- 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：O641.4
- 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：190k
- 原文格式：D
- 会议级别：全国
摘要
Transition metal carbonyl clusters play important roles in organometallic chemistry synthesis and catalysis.Dinuclear metal carbonyl complexes are the simplest representatives of transition metal carbonyl clusters for the study of the nature of metal-carbonyl and metal-metal bonding and have been extensively studied both experimentally and theoretically.Here we report a combined infrared spectroscopic and theoretical study on hetero dinuclear transition metal carbonyl cations MM'(CO)_n~+(M,M'=Fe,Co,Ni,Cu;n=7 or 8)in gas phase.The infrared spectra of mass-selected ions are measured via infrared photodissociation spectroscopy in the carbonyl stretching frequency region.The structures are established by comparison of the experimental spectra with the simulated spectra derived from density functional calculations.The FeM'(CO)_8~+(M'=Co,Ni,Cu)complexes are determined to have eclipsed(CO)_5Fe-M(CO)_3 structures,while the MCu(CO)_7~+(M=Co,Ni)ions are determined to have staggered(CO)_4M-Cu(CO)_3 structures with all of the carbonyl ligands terminally bonded.According to NBO and EDA-NOCV analysis,the positive charge is mainly distributed on the metal with larger atomic number.For all of the complexes studied,an a-type dative bond is formed between the two metal centers.And the interactions between the vicinal carbonyls on iron and the other metal also contribute to the stabilization in FeCo(CO)_8~+and FeNi(CO)_8~+.
Transition metal carbonyl clusters play important roles in organometallic chemistry synthesis and catalysis.Dinuclear metal carbonyl complexes are the simplest representatives of transition metal carbonyl clusters for the study of the nature of metal-carbonyl and metal-metal bonding and have been extensively studied both experimentally and theoretically.Here we report a combined infrared spectroscopic and theoretical study on hetero dinuclear transition metal carbonyl cations MM'(CO)_)n~+(M,M' = Fe,Co,Ni,Cu;n = 7 or 8) in gas phase.The infrared spectra of mass-selected ions are measured via infrared photodissociation spectroscopy in the carbonyl stretching frequency region.The structures are established by comparison of the experimental spectra with the simulated spectra derived from density functional calculations.The FeM'(CO)_8~+(M' = Co,Ni,Cu) complexes are determined to have eclipsed(CO)_5Fe-M(CO)_3 structures,while the MCu(CO)_7~+(M = Co,Ni) ions are determined to have staggered(CO)_4M-Cu(CO)_3 structures with all of the carbonyl ligands terminally bonded.According to NBO and EDA-NOCV analysis,the positive charge is mainly distributed on the metal with larger atomic number.For all of the complexes studied,an σ-type dative bond is formed between the two metal centers.And the interactions between the vicinal carbonyls on iron and the other metal also contribute to the stabilization in FeCo(CO)_8~+ and FeNi(CO)_8~+.
Transition metal carbonyl clusters play important roles in organometallic chemistry synthesis and catalysis.Dinuclear metal carbonyl complexes are the simplest representatives of transition metal carbonyl clusters for the study of the nature of metal-carbonyl and metal-metal bonding and have been extensively studied both experimentally and theoretically.Here we report a combined infrared spectroscopic and theoretical study on hetero dinuclear transition metal carbonyl cations MM'(CO)_)n~+(M,M' = Fe,Co,Ni,Cu;n = 7 or 8) in gas phase.The infrared spectra of mass-selected ions are measured via infrared photodissociation spectroscopy in the carbonyl stretching frequency region.The structures are established by comparison of the experimental spectra with the simulated spectra derived from density functional calculations.The FeM'(CO)_8~+(M' = Co,Ni,Cu) complexes are determined to have eclipsed(CO)_5Fe-M(CO)_3 structures,while the MCu(CO)_7~+(M = Co,Ni) ions are determined to have staggered(CO)_4M-Cu(CO)_3 structures with all of the carbonyl ligands terminally bonded.According to NBO and EDA-NOCV analysis,the positive charge is mainly distributed on the metal with larger atomic number.For all of the complexes studied,an σ-type dative bond is formed between the two metal centers.And the interactions between the vicinal carbonyls on iron and the other metal also contribute to the stabilization in FeCo(CO)_8~+ and FeNi(CO)_8~+.
引文
[1]Housecroft,C.E.Metal-Metal Bonded Carbonyl Dimers and Clusters.Oxford University Press:Oxford,U.K.1996.
[2]Zhou,M.F.;Andrews,L.;Bauschlicher,C.W.,Jr.Chem.Rev.2001,101(7):1931.
[3]Wang,G.J.;Chi,C.X.;Xing,X.P.;Ding,C.F.;Zhou,M.F.Sci.China Chem.2014,57:172.
[2]Zhou,M.F.;Andrews,L.;Bauschlicher,C.W.,Jr.Chem.Rev.2001,101(7):1931.
[3]Wang,G.J.;Chi,C.X.;Xing,X.P.;Ding,C.F.;Zhou,M.F.Sci.China Chem.2014,57:172.