Aminocarbyne ligands in organometallic chemistry

When ferrocene and diiron organometallics meet: triiron vinyliminium complexes exhibit strong cytotoxicity and cancer cell selectivity

“…The availability of up to two coordination sites by sequential displacement of carbonyl ligands is required for the construction of bridging hydrocarbyl fragments from the assembly of small molecular pieces. 22 This procedure leads to cationic [Fe I Fe I ] complexes comprising either an aminocarbyne 23 or a vinyliminium 24 as the bridging ligand (structures III and IV in Fig. 1); these complexes are amphiphilic and appreciably water-soluble, and exhibit an antiproliferative activity against cancer cell lines that depends on the ligand substituents.…”

Alkyne–alkenyl coupling at a diruthenium complex

“…[1][2][3] For instance, as two working hands compared to one single hand, dimetallic systems offer major opportunities to build and stabilize uncommon hydrocarbyl ligands via multisite bridging coordination. [4][5][6][7][8][9][10] Alkynes are useful and versatile reagents in this setting, and in particular the {M 2 Cp 2 (CO) x } scaffold (M = Fe, Ru; Cp = η 5 -C 5 H 5 ; x = 2, 3) is suitable to promote their coupling with a diversity of bridging coordinated carbon ligands, including carbonyl, 11,12 isocyanide, 13 thiocarbonyl, 14 alkylidyne 10,15,16 and alkylidene ligands, [17][18][19][20] usually via alkyne insertion into the metal-μ-carbon bond, but alternative modes are also possible. 21 The two metal coordination spheres are coordinatively and electronically saturated, therefore prior removal of one 2-electron ligand (usually, a carbon monoxide ligand) is needed to guarantee the initial η 2 -coordination of the alkyne to one metal centre, that is a preliminary, fundamental step along the coupling process.…”

A comparative structural and spectroscopic study of diiron and diruthenium isocyanide and aminocarbyne complexes

“…In 1975, Chatt, Richards, Pombeiro and co-workers reported the first synthesis of an aminocarbyne species via isocyanide protonation [1], and in the following decades the electrophilic addition to isocyanide ligands became a classical approach to access aminocarbyne complexes of a range of transition metals [2][3][4].…”

“…The alkylation of isocyanide belonging to the different [Fe 2 Cp 2 (CO) 3 (CNR)] forms converges to a single structure containing a bridging aminocarbyne ligand and, usually, the Cp ligands in cis position, Scheme 1A [8]. Such diiron aminocarbyne complexes represent in turn versatile platforms to build many organometallic architectures [4,11] with possible biological implications [12].…”