Synthesis and investigation of novel two-coordinate 1st row transition metal complexes

Tilley教授小组未来的研究将关注新型二坐标第一行过渡金属配合物的合成和研究。由于金属中心的配位数低和固有的缺电子性质，这类化合物具有非常不寻常的结构和电子性质，在催化和功能化不同类型的底物方面有望具有丰富的反应化学。然而，这些配合物的数量是有限的，特别是对于早期的过渡金属（Ti， V, Cr, Mn）。此外，双配位配合物的反应化学研究相对较少。最近，Tilley教授及其同事成功合成了一种二坐标双（氨基）镍（II）配合物。对该配位不饱和配合物的初步研究证明其催化性能与碳-碳交叉偶联和烯烃氢硅化反应有关。这些结果促使我们对这类配合物进行深入的研究。未来的工作将集中在(i)金属和配体的变化，特别是早期过渡金属Ti， V， Cr的双配位配合物的合成，（ii）它们与氧化还原，小分子活化和C-H键活化相关的反应化学，（iii） C-C交叉偶联和烯烃聚合的催化过程的建立。

Future research in the group of Prof. Tilley will concern the synthesis and investigation of novel two-coordinate 1st-row transition metal complexes. Due to the low coordination number and inherent electron deficient nature on the metal center, this class of compounds has highly unusual structural and electronic properties, and is expected to have rich reaction chemistry in terms of catalysis and functionalization of different kinds of substrates. However, the number of these complexes is strongly limited, in particular for earlier transition metals (Ti, V, Cr, Mn). In addition, the reaction chemistry of two-coordinate complexes is relatively unexplored. Recently a two-coordinate bis(amido) nickel(II) complex has been successfully synthesized by Prof. Tilley and co-workers. Preliminary studies on this coordinatively unsaturarted complex have proven its catalytic performance associated with carbon-carbon cross-coupling and olefin hydrosilation reactions. These results prompt us to do in-depth studies on this class of complexes. Future work will focus on (i) variation of metals and ligands, in particular on the synthesis of two-coordinate complexes of earlier transition metals Ti, V, Cr, (ii) their reaction chemistry associated with redox, activation of small molecules and C-H bond activation, (iii) the establishment of catalytic processes for C-C cross coupling and olefin polymerization.