Against the Norm: Non Irving-Williams Transmetalation in Transition Metal Dimers

Sidney S Woodhouse; Tyson N Dais; Alvaro Etcheverry-Berríos; Euan K Brechin; Joseph R Lane; Paul G Plieger

doi:10.1021/acs.inorgchem.2c03113

Against the Norm: Non Irving-Williams Transmetalation in Transition Metal Dimers

Inorg Chem. 2022 Nov 7;61(44):17819-17827. doi: 10.1021/acs.inorgchem.2c03113. Epub 2022 Oct 25.

Authors

Sidney S Woodhouse¹, Tyson N Dais¹, Alvaro Etcheverry-Berríos², Euan K Brechin², Joseph R Lane³, Paul G Plieger¹

Affiliations

¹ School of Natural Sciences, Massey University, Private Bag 11 222, Palmerston North4410, New Zealand.
² EaStCHEM School of Chemistry, The University of Edinburgh, David Brewster Road, EdinburghEH93FJ, Scotland, U.K.
³ Department of Chemistry, School of Science, University of Waikato, Private Bag, Hamilton3105, New Zealand.

PMID: 36282592
DOI: 10.1021/acs.inorgchem.2c03113

Abstract

We report the synthesis and characterization of three dinuclear 3d3d' complexes, CuCu ( $[C u_{2}^{I I} L {({N O}_{3})}_{2}]$ ), MnMn ( $[M n_{2}^{I I} L {(M e O H)}_{2} {({N O}_{3})}_{2}]$ ), and CuMn ([Cu^IIMn^IIL(NO₃)₂]), that utilize the ligand, H₂L (6,6'-dimethoxy-2,2'-[(1,3-propylene)dioxybis(nitrilomethylidyne)]diphenol). The relative stabilities of these complexes were investigated using experimental and computational techniques, revealing a non-Irving-Williams transmetalation, whereby a Mn^II ion can displace a Cu^II ion from its binding pocket in CuCu to yield the more stable CuMn complex. Magnetic characterization of the reported complexes revealed an unexpected ferromagnetic coupling between the two Cu^II ions of CuCu with J = +63.0 cm^-1.