Silicon compounds of neon and argon.
Silicon compounds of neon and argon.
复制标题
氖气和氩气的硅化合物。
DOI：
10.1002/anie.200903706
复制
发表时间：
2009
影响因子：
--
通讯作者：
D. Schröder
中科院分区：
文献类型：
--
作者：
J. Roithová;D. Schröder
稀有气体化合物于1962年首次发现[1]，至今仍受到人们的持续关注。近年来，通过低温基质中的光化学反应生成各种新的惰性气体化合物，进一步推动了这一研究领域的发展。[2-4]稀有气体化学中仍然存在的挑战是形成新的稀有气体杂原子键，其中硅被提出作为特别有趣的情况，以及产生较轻的稀有气体氩和氖的新化合物。[4，5]在此，我们通过使用SiF 3 2+阳离子作为超亲电试剂来解决这两个问题[6，7]，所述超亲电试剂具有对于生成稀有气体化合物特别有利的性质。在2006年，我们建议可以将气态指示物用于此目的。[8]虽然我们确实设法产生有机分子气体化合物ArCH 2+和ArC 2 H 2+最近使用这种方法，化学产率是令人惊讶的低。[9，10]同样，在中性CO与Ar 2+和中性氩与CO2+的碰撞驱动反应中观察到少量双原子二价离子ArC 2+。[11用于攻击稀有气体的更有效的双阳离子试剂不仅必须是有效的超亲电体，而且它还需要满足以下要求：1）它应该具有可以被稀有气体原子取代而不涉及显著的动力学势垒（例如均裂键断裂）的潜在离去基团; 2）稀有气体的优选氧化态[13]意味着可以预期偶数电子化合物的稳定性增加;对于均裂，双阳离子试剂应该是自由基; 3）为了防止在将键均裂到离去基团期间的电子转移过程（其将提供开壳惰性气体化合物），离去基团应具有高电离能（IE）;（4）
Noble gas compounds, which were first discovered in 1962,[1] still receive continuous interest. In recent years, this field of research experienced an additional boost by the generation of a variety of new noble gas compounds by photochemical reactions in low-temperature matrices.[2–4] Challenges in noble gas chemistry that still remain are the formation of new noble gas heteroatom bonds, in which silicon has been raised as a particularly interesting case, and the generation of new compounds of the lighter noble gases argon and neon.[4, 5] Herein, we address both issues by the use of the SiF3 2+ dication as a superelectrophilic reagent [6, 7] with particularly favorable properties for the generation of noble gas compounds.It is obvious that the involvement of the inert noble gases in covalent chemical bonds requires strong oxidation agents, such as F2; in 2006, we suggested that gaseous dications may be used for this purpose.[8] Although we indeed managed to generate the organonoble gas compounds ArCH2+ and ArC2H2+ recently using this approach, the chemical yields were disappointingly low.[9, 10] Similarly, small amounts of the diatomic dication ArC2+ had been observed in collisionally driven reactions of neutral CO with Ar2+ and of neutral argon with CO2+.[11, 12] A more efficient dicationic reagent for the attack of noble gases must not only be a potent superelectrophile, but it also needs to meet the following requirements: 1) It should possess a potential leaving group that can be replaced by a noble gas atom without a significant kinetic barrier being involved, such as a homolytic bond cleavage; 2) the preferred oxidation states of noble gases [13] mean that increased stabilities can be expected for even-electron compounds; for homolytic cleavage, the dicationic reagent should be a radical; 3) to prevent electron transfer processes during homolysis of the bond to the leaving group, which would afford an open-shell noble gas compound, the leaving group should have a high ionization energy (IE); and 4) the
乙炔双标与稀有气体反应生成有机稀有气体双标 HCCRg2（Rg = Ar 和 Kr）。
DOI：
10.1039/b810398d
发表时间：
2008
期刊：
PCCP
影响因子：
--
作者：
Ascenzi D
通讯作者：
Ascenzi D