Carbon nitride as a ligand: edge-site coordination of ReCl(CO)₃-fragments to g-C₃N₄

Abstract

IR spectroscopy and model structural studies show binding of ReCl(CO)3-fragments to carbon nitride (g-C3N4) occurs via κ2 N,N′ bidentate coordination.

Carbon Nitride as a Ligand: Selective Hydrogenation of Terminal Alkenes Using [(η5‐C5Me5)IrCl(g‐C3N4‐κ2N,N’)]Cl

“…Reported BE for [Cp*Ir(bipy)Cl]Cl} and related triazine‐bipyridine} and phenanthroline frameworks, coordinating [Cp*IrCl]+ moieties all give BE of 62.1 and 65.1 eV compared to BE of 62.3 and 65.2 eV for the more directly relevant a heptazine framework analogue . These data indicate less electron density is donated by the heptazine and related g‐C 3 N 4 ligand in comparison to other common κ 2 N , N donor ligands and support the hypothesis that κ 2 N , N binding to edge sites of g‐C 3 N 4 is relatively weak . The BE of the precursor [Cp*IrCl] 2 (61.8 and 64.8 eV, Figure S1c) are clearly distinct from 1 and 2 showing that reaction between [Cp*IrCl] 2 and g‐C 3 N 4 has occurred and not simply adsorption.…”

“…An estimated diameter of 6.5 Å for [Cp*IrCl] + , based on the X‐ray single crystal structure of 3 limits coordination to exposed edge sites on the surface of the material because coincident g‐C 3 N 4 plane edges would be sterically too hindered. The iridium loading of 1.34 wt % compares to 7.34 wt % rhenium loading for [ReCl(CO) 3 (g‐C 3 N 4 ‐κ 2 N , N’ )], where the estimated diameter of the ReCl(CO) 3 moiety is 5.5 Å, significantly smaller than [Cp*IrCl] + . The implication is that lower loading is associated with restricted access to additional potential binding sites indicating that steric non‐covalent interactions control loading of the metal complex.…”

“…More recently, we have demonstrated the selective functionalization of g‐C 3 N 4 via direct coordination of a metal complex fragment (Figure d) . Reaction between [Re(CO) 5 Cl] and g‐C 3 N 4 gave [ReCl(CO) 3 (g‐C 3 N 4 ‐κ 2 N , N’ )], where N , N’ ‐bidentate coordination of Re was assigned based on the IR spectroscopic characteristics of the carbonyl ligands.…”

A Tour‐Guide through Carbon Nitride‐Land: Structure‐ and Dimensionality‐Dependent Properties for Photo(Electro)Chemical Energy Conversion and Storage

“…Nevertheless, recent reports on grafting metal complexes onto melon suggest that it may be feasible for the heptazine nitrogens to coordinate with, for example, metal complexes of iridium [66] and rhenium. [67] Several strategies based on rational modification of the carbon nitride structure and/or morphology can also be pursued to overcome these c) a copper(II) melamine complex [60] (top) and a zinc melam complex [7a] (bottom); d) potassium tricyanomelaminate, [61] (potassium shown as white circles); and e) copper melonate [62] (top), lanthanum melonate, [63a] (middle) and zinc cyamelurate [64] (bottom). a) Reproduced with permission.…”

Synthesis, Spectral, and X-ray Structural Characterization of Mixed Tetraamine-Barbitone Nickel (II) Complex Grafted g-C3N4 for Oxidative Stress and Cytotoxic Activities

“…The polymeric carbon nitride (g-C 3 N 4 ) have been developed to be effective and environmentally nonthreatening catalysts. Immobilization of coordinated compounds on g-C 3 N 4 [11][12][13][14][15] enhances its photocatalytic activity. Moreover, its carbon structure with ordered nitrogen atoms arrangements not only improves its electronic and catalytic properties but also creates electrons and holes once visible light absorption [16][17][18].…”