New reactivity of late 3d transition metal complexes in catalytic reactions of alkynes

Abstract

Late 3d metals such as iron, cobalt, nickel, and copper are abundantly present in the Earth's crust and they are produced in huge quantities in the mining industry. Often, these inexpensive metals exhibit unique or special reactivities in catalytic reactions as compared with expensive noble metals such as palladium, iridium, and rhodium. The novel reactivities of 3d metal complexes originate from their unique physical and atomic properties as compared with heavier 4d/5d congeners: smaller ionic and covalent radii, contracted 3d orbitals of smaller sizes and lower energies, lower values of Pauli electronegativity, etc. This review summarizes the recent progress in late 3d transition metal-catalyzed transformations of alkynes. We organize catalytic examples according to each type of novel elementary reactivity exhibited by 3d metal complexes. Each section includes a description of the unique reactivity of the 3d metals, the atomic and theoretical basis of the reactivity and illustrations of catalytic examples: (1) single electron transfer from low-valent metal complexes to alkyl halides, (2) facile reductive elimination from nickel(III), (3) facile reductive elimination from copper(III), (4) cis-to-trans isomerization of alkenyl metal complexes after syn-insertion, (5) ligand-to-ligand hydrogen transfer, (6) hydrogen atom transfer from hydride complexes and (7) protonation of nickel metallacyclopropenes.