Metathesis reactivity of bis(phosphinite) pincer ligated nickel chloride, isothiocyanate and azide complexes

Abstract A series of nickel pincer complexes of the type [4-Z-2,6-(R 2 PO) 2 C 6 H 2 ]NiX (R =  t Bu, i Pr, Ph; Z = H, CO 2 Me; X =  N CS, N 3 ) have been synthesized from the reactions of the corresponding nickel chloride complexes [4-Z-2,6-(R 2 PO) 2 C 6 H 2 ]NiCl and potassium thiocyanate or sodium azide. X-ray structure determinations of these complexes have shown that the thiocyanate ion binds to the nickel center through the nitrogen. A comparable Ni–N bond length (approx. 1.87 A for the isothiocyanate complexes and 1.91 A for the azide complexes) and an almost identical Ni–C ipso bond length (approx. 1.89 A) have been observed for these complexes. Metathesis reactivity of [4-Z-2,6-(R 2 PO) 2 C 6 H 2 ]NiCl and ligand exchange reactions between the nickel isothiocyanate and nickel azide complexes have been investigated. The metathesis reactions with thiocyanate/azide complexes are faster with a less electron rich and more sterically accessible nickel center. The thermodynamic stability of these nickel complexes has been rationalized using hard-soft acid-base theory (HSAB theory); a harder ligand prefers a less electron rich nickel center. These experimental results have been supported by quantum chemical analysis of the coordinating nitrogen atoms in SCN – and N 3 − .