Cyanoferrocenes as redox-active metalloligands for coordination-driven self-assembly

Abstract

An improved synthetic protocol to cyanoferrocenes is presented along with their coordination to copper(i) salts. The redox and structural properties of the complexes are investigated, alongside the lability of the metalloligands.

Tricyanated Ferrocenes; Isolation, structure, electrochemistry and DFT calculations

“…The electrochemistry of cyanoferrocenes was investigated by cyclic voltammetry in previous publications. Half‐wave potentials (relative to the FcH/FcH + couple) for monocyanoferrocene at 436 mV (1.0 mmol/L in CH 2 Cl 2 with 0.1 mmol/L NBu 4 B(C 6 F 5 ) 4 as supporting electrolyte, scan rate 100 mV/s) [10d] and for the dicyanoferrocene compound at either 767 mV (concentration not given, in CH 2 Cl 2 with 0.1 mmol/L NBu 4 PF 6 as supporting electrolyte, scan rate 100 mV/s) [12a] or 860 mV (1.0 mmol/L in CH 2 Cl 2 with 0.1 mmol/L NBu 4 B(C 6 F 5 ) 4 as supporting electrolyte, scan rate 100 mV/s) [17b] were reported.…”

“…[10] Cyanoferrocene 1 c, first reported in 1957, [11] is a generally wellstudied compound (156 references according to SciFinder n , accessed on January 10th, 2022), and many synthetic approaches have been reported, with many different starting materials, and yields between 5 and 90 %. [9,[11][12][13][14][15][16][17][18][19][20] . In contrast to this, there are rather few reports on the three isomeric dicyanoferrocenes (24 entries on 1,1'-, two entries on 1,2-and one on 1,3-dicyanoferrocene) and none on ferrocenes with three or more cyano substituents.…”

The core of the matter – arene substitution determines the coordination and catalytic behaviour of tris(1-phosphanyl-1′-ferrocenylene)arene gold(i) complexes

“…Table S3 †) are closer to the ideal 180°t han those found in [1b(Au)]OTf, most likely because the 1,3,5-tris(ferrocenyl)arene-derived ligand structure itself does not impose any steric restrictions anymore. The individual Even though the formation of this CP was not intended and its preparation suffers from poor reproducibility, redox-active ferrocene-derived CPs have recently attained great interest for the insight into molecular architecture and self-assembly [75][76][77] they provide as well as for their potential applications in catalysis, 78,79 non-linear optics, and molecular magnetism. 77 Following the classification of Mochida, {[(1c) 2 (Au) 3 ](OTf ) 3 } n is a one-dimensional main-chain CP derived from a neutral ligand.…”

Synthesis, Molecular and Crystal Structures of Some Monocyanocymantrenes

“…Although they are known for a while [11], only very few studies devoted to applications have been reported [12]. So far, the main interest seems to have been in their use as complex ligands [13][14][15]. This is also true, when it comes to crystal structure determinations.…”