Accessing Alkyl- and Alkenylcyclopentanes from Cr-Catalyzed Ethylene Oligomerization Using 2-Phosphinophosphinine Ligands
作者:Robert J. Newland、Alana Smith、David M. Smith、Natalie Fey、Martin J. Hanton、Stephen M. Mansell
DOI:10.1021/acs.organomet.8b00063
日期:2018.3.26
2-phosphinophosphinines were compared to those of bidentate diphosphorus ligands computationally, contextualizing them in the ligand knowledge base for bidentate P,P donor ligands (LKB-PP), and were found to occupy an area of ligand space adjacent to Ar2PN(R)NAr2 ligands that have been successfully used in ethylene oligomerization reactions, but with well-separated properties in the second principal component. Testing
将2-膦膦膦2-PPh 2 -3-Me-6-SiMe 3 -PC 5 H 2与盐酸进行甲硅烷基化反应,得到2-PPh 2 -3-Me-PC 5 H 3,表明该双齿的后期修饰杂环配体。这些配体的第6族金属羰基配合物表明κ 2结合和65.1-68.3非常小咬角°,并且还证明2- phosphinophosphinines供体性质可通过森达的存在容易地调谐3基团,其产生更多的π接受的次膦配体。通过计算比较了2-膦基膦的性质与双齿二磷配体的性质,在双齿P,P供体配体(LKB-PP)的配体知识库中对它们进行了上下文描述,发现它们占据了与Ar 2相邻的配位空间PN(R)NAr 2配体已成功用于乙烯低聚反应,但在第二主成分中具有良好的分离特性。在Cr催化的乙烯低聚反应中测试2-膦基膦亚胺显示出与标准PNP配体的主要区别,因为形成了高比例的烷基和烯基环戊烷。这表明2-膦基膦亚甲基的不同供体性质影响在金属环