Supported phosphine-Rh systems, prepared in situ from silica-supported bridgehead monophosphines and [Rh(OH)(cod)]2, have enabled ortho-selective C-H borylation for a range of arenes containing nitrogen-based directing groups. The regioselectivity was excellent with various N-directing groups, including saturated and unsaturated N-heterocycles, tert-aminoalkyl groups, and iminetype C-N double bonds. The reaction showed significant tolerance toward steric repulsion around the reacting C-H bond. This Rh catalysis complements the Jr-catalyzed orthoborylation, which is effective for arenes with oxygen-based directing groups.
Phosphorus or nitrogen – the first phosphatriptycene in coordination polymer chemistry
acceptor character of the phoshatriptycene moiety. When both the chloride salts of hard ZnII and soft AuI cations are available for coordination, TRIP-Py acts as selective ditopic linker in the discrete trinuclear mixed-metal complex [ZnCl2(TRIP–PyAuCl)2]. For CdII, a cation with intermediate Pearson character, selectivity withers, and a monometallic coordinationpolymer is obtained. Its significantly elongated
Phosphasilatriptycene、亚苯基间隔基和吡啶基部分代表了 TRIP-Py 的构建块,这是第一个具有 phoshatriptycene 支架的异源双位配体。位于扁长 TRIP-Py 分子两端的 P 和 N 供体位点选择性地配位与其 Pearson 特征匹配的金属阳离子。较硬的吡啶供体与 Zn II结合,较软的磷供体与 Pt II、Hg II和 Au I结合。后者中非常短的 Au-P 键突显了磷酸三蝶烯部分的良好 π 受体特性。当硬 Zn II和软 Au I的氯化物盐阳离子可用于协调,Trip-py充当离散的三核混合金属复合物[ZnCl 2(Trip – Pyaucl)2 ]中的选择性二置连接器。对于 Cd II,获得了具有中等 Pearson 特性、选择性消失和单金属配位聚合物的阳离子。然而,其显着拉长的 Cd-P 配位键强调了 Cd II对较硬的 N 供体的偏好。当 Zn