CNRS, Chimie UMR 7177, Laboratoire de Chimie de Coordination, Université de Strasbourg, 4 rue Blaise Pascal, 67081 Strasbourg Cedex, France.
Inorganic Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimiopolis Zografou, 15771 Athens, Greece.
Chem Rev. 2021 Jul 14;121(13):7346-7397. doi: 10.1021/acs.chemrev.0c01197. Epub 2021 Jun 3.
The chemistry of discrete molecular chains constituted by metals in low oxidation states, displaying metal-metal proximity and stabilized by suitable metal-bridging, assembling ligands comprising at least one soft donor atom is comprehensively reviewed; complexes with a single (hard or soft) bridging atom (., μ-halide, μ-sulfide, or μ-PR .) as well as "closed" metal arrays (that fall in the realm of cluster chemistry) are excluded. The focus is on transition metal-based systems, with few excursions to cases combining transition and post-transition elements. Most relevant supporting ligands have neutral C, P, O, or S donor (mainly, N-heterocyclic carbene, phosphine, ether, thioether) or anionic donor (mainly phenyl, ylide, silyl, phosphide, thiolate) groups. A supporting-ligand-based classification of the metal chains is introduced, using as the classifying parameter the number of "bites" (., ligand bridges) subtending each intermetallic separation. The ligands are further grouped according to the number of donor atoms interacting with the metal chain (called denticity in the following) and the column of the Periodic Table to which the set of donor atoms belongs (in ascending order). A complementary metal-based compilation of the complexes discussed is also provided in a concise tabular form.
综述了由低氧化态金属构成的离散分子链的化学，这些分子链显示出金属-金属接近性，并通过合适的金属桥联组装配体得到稳定，这些配体至少包含一个软供体原子；排除了具有单个（硬或软）桥接原子（例如μ-卤化物、μ-硫属元素或μ-PR ）和“封闭”金属阵列（属于簇化学领域）的配合物。重点是基于过渡金属的系统，很少涉及到过渡金属和后过渡金属结合的情况。大多数相关的支撑配体具有中性 C、P、O 或 S 供体（主要是 N-杂环卡宾、膦、醚、硫醚）或阴离子供体（主要是苯基、叶立德、硅基、磷化物、硫醇盐）基团。根据每个金属间间隔的“咬口数”（即配体桥），引入了基于支撑配体的金属链分类，将配体进一步根据与金属链相互作用的供体原子数（在下面称为齿合度）和供体原子所属的元素周期表列（按升序）进行分组。还以简洁的表格形式提供了所讨论配合物的补充基于金属的汇编。
