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Lanthanides and actinides: Annual survey of their organometallic chemistry covering the year 2016

机译：镧系和act系元素：涵盖其2016年的有机金属化学年度调查

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This review summarizes the progress in organo-f-element chemistry during the year 2016. In some ways, the organo-f-element chemistry published in 2016 differs from that of previous years. For example, gasphase reactions of laser-vaporized lanthanide atoms with small unsaturated organic molecules have been the subject of several interesting experimental and theoretical studies. Various unstable homoleptic and heteroleptic gas-phase species have been generated that way and studied by spectroscopic methods. Notable in this area are e. g. the methylene derivative CH2CeF2, the ceracyclopropene Ce(C2H2), the perdeuterated yttrium phenyl cation [Y(C6D5)](+), and unusual scandium carbonyl complexes such as OScCO and OCScCO3. Remarkable divalent lanthanide alkyls and carbene complexes have also been described in 2016. A continuing trend for many years which continued into 2016 was the investigation of highly reactive lanthanide alkyl complexes supported by non-cyclopentadienyl ligands (e. g. amidinates, beta-diketiminates etc.). Many of these complexes found useful applications in homogeneous catalysis. Interesting reactivities have been reported e. g. for the first non-pincer-type mononuclear scandium alkylidene complexes and a series of mixed methyl/methylidene trinuclear rare-earth metal complexes. The isolation, structure and reactivity of a unique scandium boryl oxycarbene complex as well as the first molecular polyarsenides of the rare-earth elements have also been reported. Several examples of macrocyclic compounds ("giant lanthanide wheels") have been prepared with the use of specially designed Nchelating ligands. New chemistry has been developed around "samarocene oxide", Cp/2Sm-O-Cp/2 (Cp*=pentamethylcyclopentadienyl) which is generally considered as an undesired decomposition product of the highly air-sensitive divalent samarocene Cp-2*Sm(THF) 2, and novel 1,1'-diphospaplumbocenes have been synthesized and subsequently employed as phospholyl ligand transfer reagents in organothulium chemistry. Synthesis and derivative chemistry of an Yb(II) triple-decker complex with the l-bridging naphthalene dianion have been investigated, including in formation of an unusual trinuclear Yb(II) complex with a l-bridging P-7(3) ligand. The cyclooctatetraenyl dianion (COT) continued to be a versatile building block for the synthesis of new half-sandwich, sandwich, and inverse sandwich complexes. Significant progress has also been made in the field of endohedral metallofullerenes, including the synthesis and characterization of an unusual non-isolated pentagon rule metallic carbide clusterfullerene containing a seven-membered ring, Sc2C2@C-s(hept)-C-88. In the field of heterometallic organolanthanide complexes, novel inclusion complexes of the composition (Cp/2Yb) 2(Cp2M) (Cp = cyclopentadienyl; M = V, Cr, Fe, and Co) have been isolated in the solid state. Once again, an impressive number of interesting contributions have been published in 2016 in the field of organolanthanide catalysis, with an emphasis on Ln-catalyzed olefin and diene polymerization.
机译：这篇综述总结了2016年有机氟化学的进展。在某些方面，2016年发表的有机氟化学与往年有所不同。例如，激光蒸发的镧系元素原子与小的不饱和有机分子的气相反应已成为一些有趣的实验和理论研究的主题。这样就产生了各种不稳定的均相和异相气相物质，并通过光谱方法进行了研究。在这个领域值得注意的是e。 G。亚甲基衍生物CH2CeF2，铈环丙烯Ce（C2H2），氘化的钇苯基阳离子[Y（C6D5）]（+）和不寻常的羰基dium羰基配合物，例如OScCO和OCScCO3。在2016年也描述了显着的二价镧系元素烷基和卡宾配合物。一直持续到2016年的多年趋势是研究由非环戊二烯基配体（例如a酰胺，β-二酮等）支撑的高反应性镧系元素烷基络合物。这些络合物中的许多发现在均相催化中有用的应用。已经报道了有趣的反应。 G。用于首个非钳型单核alkyl亚烷基配合物和一系列混合的甲基/亚甲基三核稀土金属配合物。还已经报道了独特的scan硼氧碳烯配合物以及稀土元素的第一分子聚砷化物的分离，结构和反应性。大环化合物（“大型镧系元素轮”）的几个例子已经通过使用特殊设计的螯合配体来制备。已经围绕“三茂铁氧化物” Cp / 2Sm-O-Cp / 2（Cp * =五甲基环戊二烯基）开发了新化学方法，该化合物通常被认为是高度空气敏感性的二价三茂铁Cp-2 * Sm（THF）的不希望有的分解产物。 ）2，并且已经合成了新颖的1,1'-二phospaplumbocenes，随后将其用作有机th化学中的磷酰基配体转移试剂。已经研究了具有I桥联萘二价阴离子的Yb（II）双层配合物的合成和衍生化学，包括形成具有I桥联的P-7（3）配体的不寻常的三核Yb（II）配合物。环辛二烯基二价阴离子（COT）仍然是合成新的半三明治，三明治和反三明治复合物的通用结构单元。在内面金属富勒烯领域中也取得了重大进展，包括合成和表征了一个不寻常的，非孤立的五边形规则金属碳化物簇富勒烯，它含有一个七元环，Sc2C2 @ C-s（hept）-C-88。在杂金属有机镧系元素络合物领域，已分离出固态的（Cp / 2Yb）2（Cp2M）（Cp =环戊二烯基； M = V，Cr，Fe和Co）的新型包合物。 2016年，在有机镧系元素催化领域再次发表了令人印象深刻的许多有趣的贡献，重点是Ln催化的烯烃和二烯聚合。

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