摘要：The rational design of efficient single-atomic(SA)catalysts is essential and highly desirable but impeded by the lack of sufficient acknowledge between structure and *** this end,it is critical to clarify the effect of the coordination structure of active metal centers on the catalytic activities for the design of such ***,we report that different coordination structures of SA Pt catalysts can dramatically influence their activities for anti-Markovnikov hydroboration of *** with the other two coordination structures(Pt-N4 and Pt-O2),the SA Pt species coordinated with three O atoms(Pt-O3)display the highest turnover number value of 3288 for the hydroboration reaction to access the important alkylboronic *** functional theory calculations reveal that a superior catalytic activity can be expected for alkene hydroboration over the three O coordinated Pt species due to the lowest reaction energy(ΔG)limiting step from the reaction phase diagram.

摘要：In contrast to heterogeneous network frameworks(e.g.,covalent organic frameworks and metal‐organic frameworks)and porous organic polymers,porous organic cages(POCs)are soluble molecules in common organic solvents that provide significant potential for homogeneous ***,we report a triphenylphosphine‐derived quasi‐porous organic cage(denoted as POC‐DICP)as an efficient organic molecular cage ligand for Rh/PPh_(3) system‐catalyzed homogeneous hydroformylation ***‐DICP not only displays enhanced hydroformylation selectivity(aldehyde selectivity as high as 97%and a linear‐to‐branch ratio as high as 1.89)but can also be recovered and reused via a simple precipitation method in homogeneous reaction *** speculate that the reason for the high activity and good selectivity is the favorable geometry(cone angle=123.88°)and electronic effect(P site is relatively electron‐deficient)of POC‐DICP,which were also demonstrated by density functional theory calculations and X‐ray absorption fine‐structure characterization.