New frontiers in the chemistry of late metal pincer complexes

这个无机、生物无机和有机金属化学项目的奖项支持布兰代斯大学的奥列格·奥泽罗夫博士探索一类新的基于二芳胺的“钳形”PNP配体与9和10族金属的有机金属化学，以开发新的、优越的互补C-C和c -杂原子偶联反应催化剂。该项目的第一部分还包括对固态N-C氧化加成反应动力学的跨学科研究。第二部分涉及基于Ni（可能还有Pd或Pt）的PNP配合物的新型Lewis酸催化剂的开发。新颖的部分原因在于[(PNP)M]+阳离子的不同寻常的刘易斯酸度，但也在于镍的使用，镍是一种未被充分利用的金属，在钳基催化中，它比更常用的Pd更便宜，也更环保。第二部分还包括非常不寻常的，明显的三坐标，顺磁性Pd（II）和Pt（II）的化合物的研究。三坐标Pd和Pt化合物在催化过程中经常被用作中间体，但这些物质的三重态自旋态的合理性尚未被揭示。更广泛的影响是培训研究生和本科生，特别是妇女，并与来自三个非博士学院的研究人员建立合作关系。Ozerov博士还与波士顿学院的William Armstrong博士合作，将波士顿地区无机化学（BRIC）会议的范围扩展到波士顿大都会地区以外，并扩展到非博士学位授予机构。

This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports Dr. Oleg Ozerov at Brandeis University to explore the organometallic chemistry of a new class of diarylamido-based "pincer" PNP ligands with group 9 and 10 metals to develop of new, superior catalysts for complementary C-C and C-heteroatom coupling reactions. The first section of the project also includes an interdisciplinary study of the kinetics of the solid-state N-C oxidative addition reaction. The second section concerns the development of new Lewis acid catalysts based on the PNP complexes of Ni (and possibly Pd or Pt). The novelty lies partly in the unusual Lewis acidity of [(PNP)M]+ cations but also in the use of Ni, an underutilized metal in pincer-based catalysis, that is cheaper than the more commonly-used Pd and also more environmentally benign. The second section alsoincludes the investigation of very unusual, apparently three-coordinate, paramagnetic compounds of Pd(II) and Pt(II). Three-coordinate Pd and Pt compounds are often invoked as intermediates in catalytic processes, but the plausibility of the triplet spin state for such species has not yet been brought to light.Broader impacts are in the training of graduate and undergraduate students, particularly women, and the establishment of collaborations with researchers from three non-PhD schools. In collaboration with Dr. William Armstrong at Boston College, Dr. Ozerov has also expanded the Boston Regional Inorganic Chemistry (BRIC) meetings sphere of reach outside of the metro Boston area and also to non-PhD granting institutions.