More Like this

1. Structure, Magnetism, and Multi-electron Reduction Reactivity of the Inverse Sandwich Reduced Arene La 2+ Complex [{[C 5 H 3 (SiMe 3 ) 2 ] 2 La} 2 (μ-η 6 :η 6 -C 6 H 6 )] 1–

   https://doi.org/10.1021/acs.organomet.8b00523  

   Palumbo, Chad T. ; Darago, Lucy E. ; Dumas, Megan T. ; Ziller, Joseph W. ; Long, Jeffrey R. ; Evans, William J. ( September 2018 , Organometallics)
2. Synthesis and Reactivity of Functionalized Dimethylgermyl Complexes of the Formula (η 5 -C 5 H 5 )Re(NO)(PPh 3 )(GeMe 2 X); Equilibria Involving the Dimethylgermylene Complex [(η 5 -C 5 H 5 )Re(NO)(PPh 3 )(=GeMe 2 )]• TfO −

   https://doi.org/10.1080/10426509408037445  

   Lee, Kenneth E. ; Gladysz, J. A. ( February 1994 , Phosphorus, Sulfur, and Silicon and the Related Elements)
3. Crystal structures of (η 4 -cycloocta-1,5-diene)bis(1,3-dimethylimidazol-2-ylidene)iridium(I) iodide and (η 4 -cycloocta-1,5-diene)bis(1,3-diethylimidazol-2-ylidene)iridium(I) iodide

   https://doi.org/10.1107/S2056989020004235  

   Bernier, Chad M. ; DuChane, Christine M. ; Merola, Joseph S. ( May 2020 , Acta Crystallographica Section E Crystallographic Communications)

   null (Ed.)

   The title complexes, (η 4 -cycloocta-1,5-diene)bis(1,3-dimethylimidazol-2-ylidene)iridium(I) iodide, [Ir(C 5 H 8 N 2 ) 2 (C 8 H 12 )]I, ( 1 ) and (η 4 -cycloocta-1,5-diene)bis(1,3-diethylimidazol-2-ylidene)iridium(I) iodide, [Ir(C 7 H 12 N 2 ) 2 (C 8 H 12 )]I, ( 2 ), were prepared using a modified literature method. After carrying out the oxidative addition of the amino acid L-proline to [Ir(COD)(IMe) 2 ]I in water and slowly cooling the reaction to room temperature, a suitable crystal of 1 was obtained and analyzed by single-crystal X-ray diffraction at 100 K. Although this crystal structure has previously been reported in the Pbam space group, it was highly disordered and precise atomic coordinates were not calculated. A single crystal of 2 was also obtained by heating the complex in water and letting it slowly cool to room temperature. Complex 1 was found to crystallize in the monoclinic space group C 2/ m , while 2 crystallizes in the orthorhombic space group Pccn , both with Z = 4. 

   more » « less
4. Thermodynamic and kinetic studies of H 2 and N 2 binding to bimetallic nickel-group 13 complexes and neutron structure of a Ni(η 2 -H 2 ) adduct

   https://doi.org/10.1039/C9SC02018G  

   Cammarota, Ryan C. ; Xie, Jing ; Burgess, Samantha A. ; Vollmer, Matthew V. ; Vogiatzis, Konstantinos D. ; Ye, Jingyun ; Linehan, John C. ; Appel, Aaron M. ; Hoffmann, Christina ; Wang, Xiaoping ; et al ( July 2019 , Chemical Science)

   Understanding H 2 binding and activation is important in the context of designing transition metal catalysts for many processes, including hydrogenation and the interconversion of H 2 with protons and electrons. This work reports the first thermodynamic and kinetic H 2 binding studies for an isostructural series of first-row metal complexes: NiML, where M = Al ( 1 ), Ga ( 2 ), and In ( 3 ), and L = [N( o -(NCH 2 P i Pr 2 )C 6 H 4 ) 3 ] 3− . Thermodynamic free energies (Δ G °) and free energies of activation (Δ G ‡ ) for binding equilibria were obtained via variable-temperature 31 P NMR studies and lineshape analysis. The supporting metal exerts a large influence on the thermodynamic favorability of both H 2 and N 2 binding to Ni, with Δ G ° values for H 2 binding found to span nearly the entire range of previous reports. The non-classical H 2 adduct, (η 2 -H 2 )NiInL ( 3 -H 2 ), was structurally characterized by single-crystal neutron diffraction—the first such study for a Ni(η 2 -H 2 ) complex or any d 10 M(η 2 -H 2 ) complex. UV-Vis studies and TD-DFT calculations identified specific electronic structure perturbations of the supporting metal which poise NiML complexes for small-molecule binding. ETS-NOCV calculations indicate that H 2 binding primarily occurs via H–H σ-donation to the Ni 4p z -based LUMO, which is proposed to become energetically accessible as the Ni(0)→M( iii ) dative interaction increases for the larger M( iii ) ions. Linear free-energy relationships are discussed, with the activation barrier for H 2 binding (Δ G ‡ ) found to decrease proportionally for more thermodynamically favorable equilibria. The Δ G ° values for H 2 and N 2 binding to NiML complexes were also found to be more exergonic for the larger M( iii ) ions. 

   more » « less
5. Ligand-Directed Reactivity in Dioxygen and Water Binding to cis -[Pd(NHC) 2 (η 2 -O 2 )]

   https://doi.org/10.1021/jacs.7b09905  

   Palluccio, Taryn D. ; Cai, Xiaochen ; Majumdar, Subhojit ; Serafim, Leonardo F. ; Tomson, Neil C. ; Wieghardt, Karl ; Cazin, Catherine S. ; Nolan, Steven P. ; Rybak-Akimova, Elena V. ; Fernández-González, Miguel Ángel ; et al ( January 2018 , Journal of the American Chemical Society)