RETRACTED: Isocyanide metal complexes in catalysis

Positional Isomers of Isocyanoazulenes as Axial Ligands Coordinated to Ruthenium(II) Tetraphenylporphyrin: Fine-Tuning Redox and Optical Profiles

“…Moreover, the 1 H NMR resonance for the H 5,7 atoms of 6-CNAz undergoes an upfield shift (−2.62 ppm) upon coordination to form (6-CNAz) 2 RuTPP greater than the upfield shift (−1.96 ppm) of the 1 H NMR signal for the H 1,3 atoms of 2-CNAz upon coordination of the latter to form (2-CNAz) 2 RuTPP. This observation is consistent with the azulenic H 5,7 atoms in the (6-CNAz) 2 RuTPP complex being in closer proximity to the porphyrin ring as compared to the azulenic H 1,3 nuclei in the (2-CNAz) 2 RuTPP complex. The single-crystal X-ray structural analyses of (2-CNAz) 2 RuTPP and (6-CNAz) 2 RuTPP confirm the above statement (vide infra).…”

“…Organic isocyanides, CN–R, are important constituents in coordination chemistry’s ligand toolbox, particularly because of their tunable steric and σ-donor/π-acceptor ratio characteristics. − Whereas the coordination of organic isocyanides to a variety of metalloporphyrins − and metallophthalocyanines − has been well-documented, combining redox noninnocent organic and organometallic isocyanides with such transition metal platforms offers additional distinct opportunities in the design of molecular wires. − Indeed, axial coordination of isocyanoferrocene and 1,1′-diisocyanoferrocene to Ru­(II)­porphyrins and phthalocyanines has been recently shown to exert unusual redox profiles of the corresponding adducts that are attractive in the context of applications in molecular electronics, including molecular wires. , Isocyanoazulenes constitute a special class of isocyanoarenes and feature the non-benzenoid aromatic substituent comprising fused five- and seven-membered sp 2 -carbon rings. The polar nature of the azulenic scaffold (ca.…”

“…29 Similar to the 1 H NMR patterns documented for other axially coordinated diamagnetic ruthenium/iron porphyrins and phthalocyanines, 33−39 The 1 H NMR patterns for the axial isocyanoazulene ligands are markedly different for the two isomers. 26 For complex (2-CNAz) 2 RuTPP, the 1 H NMR resonance for the H atoms at 1,3positions of the azulenic scaffold (H 1,3 ) is shifted −1.96 ppm (upfield), whereas the H 4,8 signal is shifted −1.43 ppm (upfield), compared to the corresponding resonances documented for the H 1,3 and H 4,8 nuclei of the free 2-CNAz ligand dissolved in the same solvent. The relatively large upfield shift of the H 1,3 resonance is consistent with the closer proximity of these azulenic H atoms to the porphyrin ring.…”

Bond Forming Reactions Involving Isocyanides at Diiron Complexes

“…As an example, isocyanide ligands have been successfully used for obtaining both carbene [8,9] and carbyne complexes [10]. In general, interest in isocyanide chemistry involving metal species is still growing [11,12]. One reason for this is a resurgent interest in isocyanides as C1 synthons driven by the development of transition-metal-catalyzed isocyanide insertion reactions [13][14][15][16].…”

Biosynthetic Routes to Natural Isocyanides

“…Since the seminal description by Gaultier in 1859 of a silver complex [all‐NC(Ag)CN], isocyanides have encountered large developments in coordination chemistry (Scheme ) . Similarly to carbon monoxide, isocyanides act as ligands (carbon side) and coordinate transition metals (Ag, Fe, Cu, Ni, Pd, Pt, Rh, Ir ··· ) Formation of coordination complexes is encountered in nature and some were isolated [ex: Cu I complex of halichonadin C (see section 7.4)] or are involved in the mechanism of action for bioactive compounds (see section 7.2).…”