Effect of isocyanide ligand on the interaction of triosmium isocyanide complexes with amines

Aminocarbyne ligands in organometallic chemistry

“…Another strategy to produce secondary aminocarbyne ligands makes use of protic species, enabling isocyanide protonation coupled to nucleophilic substitution/addition on carbonyl ligands. For instance, addition of primary amines to [Os3(CO)11(CNR)] leads to aminocarbyne and carboxamido ligands, via amine to isocyanide hydrogen transfer and nucleophilic CO-attack of the resulting amido group (Scheme 39a, compounds 91) [209,210]. Further CO substitution is possible, and the X-ray structure of [Os3(CO)9(NH2 i Pr)(μ:η 1 :η 1 -CONH i Pr)(μ-CNHPh)] (92a) is shown in Figure 15.…”

“…for the triosmium clusters 91 [209,210] and the diiron complex 85a [136]. Besides, dinuclear group 6 metal complexes with secondary aminocarbyne ligands have been invoked as intermediates in isocyanide/alkylidyne coupling reactions [218,224].…”

“…Secondary aminocarbyne moieties may be involved in intramolecular H-shift rearrangements. For example, passing the triosmium clusters 92 through a silica gel column promotes the displacement of the labile amine ligand and the subsequent formation of hydride species in 60-75% yields (Equation 17) [209,210].…”

Reactivity with Amines of Bis(cyanamide) and Bis(cyanoguanidine) Complexes of the Iron Triad

“…To the best of our knowledge, only these two isopropylamine complexes of ruthenium have been structurally characterized 20. Os‐N(isopropylamine), at 2.193(10) Å, is only slightly shorter than in the homologous ruthenium or in the cluster Os 3 (CO) 9 (NH 2 i Pr)(CONH i Pr)(C=NHPh) [2.233(12) Å]21 but slightly longer than that found in OsI 2 (CO) 2 (NH 2 i Pr)(PPh 3 ) [2.128(19) Å];22 once more to the best of our knowledge, only these two isopropylamine complexes of osmium were structurally characterized by X‐ray diffraction 20…”

Synthesis, Reactivity and Molecular Structures of Bis(diphenylphosphanyl)methane-Bridged Heterobimetallic Iron−Platinum Isocyanide Complexes: Breaking and Formation of Metal−Metal Bonds

“…Crystal Structure Determination of 2d: Collection of crystallographic data: intensity data were collected using the Ω/2Θ scan mode at 173 K. C 36 …”