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首页> 外文期刊>Coordination chemistry reviews >Matrix preparation and spectroscopic and theoretical investigation of small high oxidation-state complexes of groups 3-12, 14, lanthanide and actinide metal atoms: Carbon-metal single, double and triple bonds
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Matrix preparation and spectroscopic and theoretical investigation of small high oxidation-state complexes of groups 3-12, 14, lanthanide and actinide metal atoms: Carbon-metal single, double and triple bonds

机译：3-12、14，镧系和act系金属原子的小高氧化态配合物的基质制备以及光谱和理论研究：碳-金属单键，双键和三键

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Our first review article in 2006 outlined the observation, photochemical properties, and theoretical investigations of a new breed of small transition-metal complexes with C-M multiple bonds generated from reactions of group 4-6 metals with methane and methyl halides. Since then, numerous small high oxidation-state complexes have been provided by reactions of laser ablated group 3-12 transition metal, group 14 silicon atoms and lanthanide and actinide atoms with small organic precursors. Periodic trends in the primary products and their molecular structures and photochemistry are apparent. While no methylidyne reaction products were detected in reactions of the elements on the left and right sides of the d-block in the periodic table, they were the sole products in reactions of Re and Os. The actinide products identified are comparable to those from early transition-metal reactions. Agostic distorted molecular structures, photo-reversible conversions, vibrational frequencies, intensities and reaction paths have been theoretically investigated. These recent results show that C-H or C-X bond insertion and subsequent H or X migration to form higher oxidation-state products are a general phenomenon in most transition-metal systems, generating small relatives of the much larger analogues stabilized by ligands in solutions. (C) 2017 Elsevier B.V. All rights reserved.
机译：我们在2006年发表的第一篇评论文章概述了由4-6族金属与甲烷和甲基卤化物反应生成的，具有C-M多键的新型小型过渡金属配合物的观察，光化学性质和理论研究。从那时起，通过激光烧蚀的3-12族过渡金属，14族硅原子和镧系元素和act系元素原子与小的有机前体的反应，提供了许多小的高氧化态络合物。初级产品及其分子结构和光化学的周期性趋势是显而易见的。虽然在元素周期表中d嵌段左侧和右侧的元素反应中未发现亚甲基反应产物，但它们是Re和Os反应的唯一产物。鉴定出的系元素产物与早期过渡金属反应的结果相当。理论上研究了扭曲的分子结构，光可逆转化，振动频率，强度和反应路径。这些最新结果表明，在大多数过渡金属系统中，C-H或C-X键插入以及随后的H或X迁移以形成较高的氧化态产物是普遍现象，在溶液中配体稳定产生的较大类似物的亲戚较小。 （C）2017 Elsevier B.V.保留所有权利。

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