%0 Journal Article %J Chemistry A European Journal %D 2016 %T Metal–Metal Single Bonds with the Magnetic Anisotropy of Quadruple Bonds: A Systematic Series of Heterobimetallic Bismuth(II)–Rhodium(II) Formamidinate Complexes %A Sunderland, Travis L. %A Berry, John F. %X

The first set of five heterobimetallic MM′(form)4 (form=formamidinate) complexes containing a BiRh core has been successfully synthesized. The Bi−Rh bond lengths lie between 2.5196(6) and 2.572(2) Å, consistent with Bi−Rh single bonds. All complexes have rich electrochemistry, with the [BiRh]4+/5+ redox couples spanning approximately 700 mV and showing a strong correlation to remote ligand substitution. Visible spectroscopy showed two features for complexes 15 at approximately 459 and 551 nm, unique to BiRh paddlewheel complexes that are attributed to LMCT bands into the Bi−Rh σ* orbital. The large spin–orbit coupling (SOC) of Bi creates a massive Bi−Rh magnetic anisotropy, Δχ, approximately −4800×10−36 m3molecule−1, which is the largest value reported for any single bond to date.

%B Chemistry A European Journal %V 22 %8 11/2016 %G eng %U http://onlinelibrary.wiley.com/doi/10.1002/chem.201604007/abstract %& 18564 %R 10.1002/chem.201604007