Coordination chemistry of dialkylcyanamides: Binding properties, synthesis of metal complexes, and ligand reactivity

Highly Reactive NiII‐Bound Nitrile–Oxime Coupling Intermediates Stabilized by Substituting Conventional Nitriles with a Dialkylcyanamide

“…Despite the wealth of chemistry associated with the nucleophilic addition of the oxime HON=C functionality to the so‐called conventional nitrile NCR (R = alkyl, aryl) ligands, only a few works14,17 have explored metal‐bound dialkylcyanamides – NCNAlk 2 – as substrates for the addition. These reports indicate substantial distinctions in the reaction rates and the nature of products formed, [2e,3a,3b,14,17e–17g,18] and it means that these variances were recognized not only at the quantitative,3b,17f but also at the qualitative level when dialkylcyanamides and conventional nitrile ligands react with the same reagent in absolutely different ways giving, consequently, different products.…”

“…In continuation of our ongoing project on the chemistry of dialkylcyanamides (for our review, see ref 14…”

Platinum(II)‐Mediated Double Coupling of 2,3‐Diphenylmaleimidine with Nitrile Functionalities To Give Annulated Pentaazanonatetraenate (PANT) Systems

“…Imd does not react with uncomplexed RCN species under these reaction conditions, which provides evidence that the observed double coupling is Pt II -mediated and the promoting effect of the metal is rationalized by the activation of the NCR ligands toward nucleophilic attack [33,47,48] by Imd and also by the stabilization of the formed PANT species by the chelation.…”

“…In addition, for this work we employed Pt II compounds bearing the so-called push-pull nitriles, namely the dialkylcyanamides NCNR 2 [R 2 = Me 2 , Et 2 , (CH 2 ) 5 ]. Comparison of ligand reactivity of NCR and NCNAlk 2 species [33] constitutes one of the aims of this study.…”

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

“…[1][2][3] However, despite great progress in the field of nitrile RCN complexes, the coordination chemistry of cyanamides NϵCNR 2 (R = H, alkyl, aryl) and related cyanoguanidines NϵCN(H)C(NH 2 )=NH has been less developed and there are relatively few papers on the synthesis and reactivity of these complexes. [4][5][6][7] This is rather surprising, in view of the biological [8] and synthetic [9] interest of these amino-functionalized nitriles and the fact that studies on their coordination chemistry have revealed that NϵCNR 2 exhibits a different reactivity when compared with conventional nitriles. [10,11] We are interested in the chemistry of nitrile [12] and cyanamide [13] complexes of the iron triad and have recently reported the synthesis and reactivity towards hydrazines of the related bis(diethylcyanamide) and bis(cyanoguanidine) complexes.…”