Re^I Complexes of Pyridylphosphinines and 2,2′‐Bipyridine Derivatives: A Comparison

Abstract

The coordination chemistry of 2-(2′-pyridyl)-4,6-diarylphosphinines towards Re I has been investigated and compared to the structurally analogous 2,2′-bipyridine derivatives. The different steric properties of the chelating pyridylphosphinines with respect to substituted bipyridines lead to considerable differences in the structures of the mononuclear [a] Cl 2 ): δ = 188.1 ppm. ESI-TOF (m/z): 669.9649 (calcd.: 669.9552 g/mol) [M -CO + Na] + , 613.9751 (calcd.: 613.9659 g/mol) [M -3 CO + Na] + , 568.0624 (calcd.: 568.0476 g/mol) [M -CO -Br] + . FT-IR (solid ATR): ν (CO) 2026, 1935 (sh), 1899 cm -1 .

In-Depth Study of the Electronic Properties of NIR-Emissive κ3N Terpyridine Rhenium(I) Dicarbonyl Complexes

“…Their photophysical and electrochemical properties have been thoroughly studied − and applied in a multitude of fields such as solar energy harvesting devices and solar to chemical energy conversion, − light-emitting devices, , as well as photodynamic therapy and cellular imaging. , While the breadth of their application is large, most of the studies regarding these complexes follow the seminal work from Lehn, Meyer, and their co-workers, who showed in the 1980s that [Re­(CO) 3 (bpy)­X] complexes (where bpy is 2,2′-bipyridine and X is a halide) are able to catalyze the selective reduction of carbon dioxide into carbon monoxide either photo- or electrochemically. Their photophysical properties were also applied to photocatalytic hydrogen evolution, using the Re­(I) complex as a photosensitizer with a cobalt catalyst. , Efforts focused on tuning the photophysical properties of the complexes led to several structural variations, either by modification of the diimine core − or by introduction of other ligands such as a phosphine, − N-heterocyclic carbene, alkyne, , or isocyanide. , These complexes were also used as building blocks in supramolecular assemblies − and extended periodic structures. , …”

Overview of the Synthesis and Catalytic Reactivity of Transition Metal Complexes Based on C═P Bond Systems

“…The literature describes complexes of rhenium with a CP bond or complexes supported by a diphosphine ligand − and a few examples of complexes with a phosphaalkene ligand. In the case of manganese, there are several interesting reports that present different types of metal-phosphaalkene ligand coordination.…”

Phosphorus Analogues of [Ni(bpy)2]: Synthesis and Application in Carbon–Halogen Bond Activation

“…We have recently become interested in the coordination chemistry of the donor-functionalized phosphinine 2-(2′-pyridyl)-4,6-diphenylphosphinine ( L ), a “hybrid” P,N ligand that can be considered to be a cross between previously explored biphosphinines and the ubiquitous bipyridines. − L possesses two electronically distinct binding sitesa “soft” P and a “hard” N donor sitewhich can have a significant impact on its coordination properties and reactivity. Although a large variety of 4d and 5d transition-metal complexes of L have been prepared, syntheses of 3d metal complexes remain scarce. − Nevertheless, we have recently demonstrated that the combination of a late 3d metal with ligand L can lead to versatile coordination chemistry and, even more importantly, to useful reactivity, as exemplified by the facile cleavage of one CO bond in CO 2 by the Fe complex C (Figure ). …”