80890-35-3Relevant academic research and scientific papers
Synthesis of chelating bidentate isocyano and cyano ligands and their metal complexes
Angelici, Robert J.,Quick, Michael H.,Kraus, George A.,Plummer, Daniel T.
, p. 2178 - 2184 (1982)
Three air-stable, odorless, solid, bidentate isocyano and cyano ligands of the following structure have been prepared: (Chemical Equation Presented) Molecular models indicate that they should chelate to metals with the donor groups at 90° with respect to each other. From reactions of the diisocyano ligand DiNC, the following complexes with chelating DiNC ligands have been isolated: Cr(CO)4(DiNC), Mo(CO)4(DiNC), W(CO)4(DiNC), Mn(CO)3(DiNC)Br, CpFe(CO)(DiNC)+, and CpFe(CS)(DiNC)+. The characterization of these complexes demonstrates that DiNC can function as a chelating ligand despite its formation of a 13-member chelate ring. The t-BuDiNC ligand, which is much more soluble in organic solvents than DiNC, also gives complexes Cr(CO)4(t-BuDiNC), Mo(CO)4(t-BuDiNC), and CpFe(CS)(t-BuDiNC)+, which are more soluble than their DiNC analogues. When only one ligand in a reacting complex such as Cr(CO)5[(CH3)2CO], W(CO)5[(CH3)2CO], or W(CO)4(piperidine)2 is substitution labile, DiNC reacts to give complexes in which the isocyano donors are coordinated to separate metal atoms; the resulting bridging DiNC complexes [Cr(CO)5]2(u-DiNC), [W(CO)5]2(μ-DiNC), and [cis-W(CO)4(pip)]2(μ-DiNC) have been isolated. The dicyano ligand DiCN reacts to form the following complexes: Mn-(CO)3(DiCN)Br, CpFe(CS)(DiCN)+, and PtCl2(DiCN). These are the first examples of complexes containing a bidentate cyano ligand that chelates to a metal through the nitrogen lone pairs. The formation of PtCl2(DiCN) from equimolar PtCl2(NCPh)2 and DiCN indicates that the chelating DiCN binds more favorably to the metal than do the monodentate benzonitrile ligands. The ligands and complexes described above have been characterized by their IR, 1H and 13C NMR, and mass spectra.
