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

• A dozen new POCOP pincer nickel isothiocyanate and azide complexes were synthesized.
• Metathesis reactivity and ligand exchange reactions of these complexes were studied.
• The metathesis reaction is faster with a less electron rich nickel center.
• In competing with NCS−, N3−N3− prefers a less electron rich nickel center.
• The experimental results were supported by DFT calculations and the HSAB theory.

A series of nickel pincer complexes of the type [4-Z-2,6-(R2PO)2C6H2]NiX (R = tBu, iPr, Ph; Z = H, CO2Me; X = NCS, N3) have been synthesized from the reactions of the corresponding nickel chloride complexes [4-Z-2,6-(R2PO)2C6H2]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 Å for the isothiocyanate complexes and 1.91 Å for the azide complexes) and an almost identical Ni–Cipso bond length (approx. 1.89 Å) have been observed for these complexes. Metathesis reactivity of [4-Z-2,6-(R2PO)2C6H2]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 N3−N3−.

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