LOW-TEMPERATURE REACTIONS OF ATOMIC COBALT WITH CH2N2,CH4, CH3D, CH2D2, CHD3, CD4, H-2, D-2, AND HD

Billups WE.; Hauge RH.; Margrave JL.; Chang SC.

首页> 外文期刊>Journal of the American Chemical Society >LOW-TEMPERATURE REACTIONS OF ATOMIC COBALT WITH CH2N2,CH4, CH3D, CH2D2, CHD3, CD4, H-2, D-2, AND HD

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LOW-TEMPERATURE REACTIONS OF ATOMIC COBALT WITH CH2N2,CH4, CH3D, CH2D2, CHD3, CD4, H-2, D-2, AND HD

机译：原子钴与CH2N2，CH4，CH3D，CH2D2，CHD3，CD4，H-2，D-2和HD的低温反应

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Cobalt atoms react spontaneously with diazomethane in solid argon at 12 K to yield CoCH2, N2CoCH2, and at least two (N-2)(x)CoCH2 complexes. CH3CoH is formed when dihydrogen is cocondensed as a ternary reagent. Photolysis of CH3CoH (lambda greater than or equal to 400 nm) gives the sigma-complex Co(CH4) as a spectroscopically detectable species. Photolysis of this complex using an ultraviolet source regenerates CH3CoH. The sigma-complex has the triply degenerate v4(f2) absorption of methane at 1305.3 cm(-1) split into two peaks, suggesting C-3v symmetry. Studies using isotopically labeled methane show that these sigma-complexes do not have rigid structures. UV photolysis of a Co/H-2/Ar matrix at 12-15 K gives CoH2. Co(H-2) complexes could not be detected. Photolysis of Co/D-2/Ar and Co/DH/Ar matrices gave CoD2 and CoHD, respectively. [References: 67]

机译：钴原子在固体氩气中于12 K下与重氮甲烷自发反应，生成CoCH2，N2CoCH2和至少两个（N-2）（x）CoCH2络合物。当将二氢作为三元试剂共缩合时，会形成CH3CoH。 CH3CoH（λ大于或等于400 nm）的光解作用产生了sigma复合Co（CH4），可光谱检测到。使用紫外线源对该复合物进行光解可再生CH3CoH。 sigma-complex具有1305.3 cm（-1）处甲烷的三次简并的v4（f2）吸收，分为两个峰，表明C-3v对称。使用同位素标记的甲烷进行的研究表明，这些sigma-complexs不具有刚性结构。在12-15 K下对Co / H-2 / Ar基质进行UV光解得到CoH2。无法检测到Co（H-2）配合物。 Co / D-2 / Ar和Co / DH / Ar基质的光解分别得到CoD2和CoHD。 [参考：67]

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来源
《Journal of the American Chemical Society》 |1995年第4期|p. 1387-1392|共6页
作者
Billups WE.; Hauge RH.; Margrave JL.; Chang SC.;
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作者单位

RICE UNIV DEPT CHEM POB 1892 HOUSTON TX 77251 USA;

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收录信息美国《科学引文索引》(SCI);美国《工程索引》(EI);美国《生物学医学文摘》(MEDLINE);美国《化学文摘》(CA);
原文格式 PDF
正文语种 eng
中图分类化学;
关键词
Hydrogen-bond activation; Matrix-isolation spectroscopy; Reductive-elimination; Oxidative-addition; Metal-complexes; Methane; Carbene; Methyl; Chemistry; Alkanes;

机译：氢键活化;基体分离光谱;还原消除;氧化加成;金属络合物;甲烷;卡宾;甲基;化学;烷烃;

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机译：用CH3D，CH2D2，CHD3和CD4的OH基团反应的速率系数
2. VAPOR PRESSURE OF PARTIALLY DEUTERATED METHANES (CH3D, CH2D2, AND CHD3) [J] . Calado JCG., Daponte MN., Rebelo LPN., The Journal of Chemical Physics . 1997,第21期

机译：部分氘代甲烷（CH3D，CH2D2和CHD3）的蒸气压
3. Computing energy levels of CH4, CHD3, CH3D, and CH3F with a direct product basis and coordinates based on the methyl subsystem [J] . Zhao Zhiqiang, Chen Jun, Zhang Zhaojun, The Journal of Chemical Physics . 2018,第7期

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4. Cobalt(Ⅱ) Complexes of Dibenzoylmethane(Hdbm): Axial Metathetical Reaction and CrystalStructures of The Complexes with Pyridine or Its Derivatives [C] . International symposium on solid state chemistry in China amp; 8th Chinese national conference on solid state chemistry and inorganic synthesis : Book of abstracts . 2002

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5. State-resolved measurements of CH4 and CHD3 dissociation on Ni (111). [D] . Huang, Yongli. 2014

机译：镍（111）上CH4和CHD3解离的状态分辨测量。
6. Dynamics of the O(3P) + CHD3(vCH = 01) reactions on an accurate ab initio potential energy surface [O] . Gábor Czakó, Joel M. Bowman 2012

机译：精确的从头算势能面上的O（3P）+ CHD3（vCH = 0.1）反应动力学
7. Absolute Raman intensities of CH4, CH3D, CH2D2, CHD3, and CD4 [O] . Bermejo Dionisio, Escribano Rafael, Orza J. M. 2013

机译：CH4，CH3D，CH2D2，CHD3和CD4的绝对拉曼强度
8. Mechanism of the Reaction CH(+4) + CH4 = CH(+5) + CH3 as a Function of Energy: Rate Constants and Product Distributions for the Reactions of CH(+4) + CD4 and CD(+4) + CH4 at 80 and 300K. [R] . Henchman, M., Smith, D., Adams, N. G., 1989

机译：反应CH（+4）+ CH4 = CH（+5）+ CH3作为能量函数的机理：CH（+4）+ CD4和CD（+4）+ CH4反应的速率常数和产物分布80和300K。

LOW-TEMPERATURE REACTIONS OF ATOMIC COBALT WITH CH2N2,CH4, CH3D, CH2D2, CHD3, CD4, H-2, D-2, AND HD

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