Synthesis of Double-Bridged Cofacial Nickel Porphyrin Dimers with 2,2'-Bipyridyl Pillars and Their Restricted Coordination Space

Akiharu Satake; Yuta Katagami; Yuki Odaka; Yusuke Kuramochi; Shohei Harada; Takaya Kouchi; Hajime Kamebuchi; Makoto Tadokoro

doi:10.1021/acs.inorgchem.0c00177

Synthesis of Double-Bridged Cofacial Nickel Porphyrin Dimers with 2,2'-Bipyridyl Pillars and Their Restricted Coordination Space

Inorg Chem. 2020 Jun 15;59(12):8013-8024. doi: 10.1021/acs.inorgchem.0c00177. Epub 2020 May 22.

Authors

Akiharu Satake^{1

2}, Yuta Katagami¹, Yuki Odaka¹, Yusuke Kuramochi^{1

2}, Shohei Harada¹, Takaya Kouchi¹, Hajime Kamebuchi^{1

3}, Makoto Tadokoro^{1

3}

Affiliations

¹ Graduate School of Science, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan.
² Department of Chemistry, Faculty of Science Division II, Tokyo University of Science, Tokyo, Japan.
³ Department of Chemistry, Faculty of Science Division I, Tokyo University of Science, Tokyo, Japan.

PMID: 32441925
DOI: 10.1021/acs.inorgchem.0c00177

Abstract

Double-bridged cofacial Ni porphyrin dimers 2 with 2,2'-bipyridyl pillars were effectively prepared by a one-step reductive homocoupling reaction of bis(chloropyridyl)-substituted Ni porphyrin derivatives followed by a specific separation of a cyanopropyl-modified silica gel column using pyridine eluent systems. The structural analyses of 2 and its Pd complex were carried out in their solid and solution states by means of X-ray single crystal analysis and NMR, respectively. The complexation of η³-allylpalladium chloride (Pd) with 2 on the spatially restricted 2,2-bipyridine moieties on 2 gave a 2:1 (Pd:2) complex, in which the 2,2'-bipyridine ligands only provided one of the N atoms on a 2,2'-bipyridine ligand to a Pd. Therefore, the 2,2-bipyridine moieties acted as a monodentate ligand.