The B3LYP and M06-L functionals with the cc-pVTZ basis set are used to study lantern-type binuclear complexes of all the first-row (3d block) metals scandium to zinc in various low-energy spin states, out of which the ground states are predicted. These complexes are studied as models using mostly the unsubstituted formamidinate ligand. For each metal, metal-metal (MM) bond lengths are related to the formal MM bond orders (zero to five), derived by MO analysis and by electron counting. The predicted ground-state spin multiplicities and MM bond lengths of the model complexes generally agree fairly well with available experimental results on substituted analogues. Finally, values of the formal shortness ratio and Wiberg index for the MM bonds in all of these complexes in all spin states studied are categorized into ranges according to the MM bond orders 0 to 5 in steps of 0.5. The trends shown validate their use in estimating intrinsic metal-metal bond strength regardless of the metal.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1021/acs.inorgchem.4c01036 | DOI Listing |
J Am Chem Soc
December 2024
College of Chemistry, Chemical Engineering and Materials Science, and State Key Laboratory of Radiation Medicine and Protection, Soochow University, Suzhou, Jiangsu 215123, P. R. China.
Phys Chem Chem Phys
December 2024
Department of Chemistry, Maynooth University, Maynooth, Co. Kildare, Ireland.
Chem Sci
November 2024
Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford South Parks Road Oxford OX1 3QR UK
We report a convenient synthesis of the zinc-boryl complex (Nacnac)ZnBpin under mild conditions formal disproportionation of bis(pinacolato)diboron(4), aided thermodynamically by B-O bond formation. This species can be isolated both base-free and as the DMAP adduct (Nacnac)Zn(DMAP)Bpin and crystallographically characterised in the latter form. Onward reactivity of the base free zinc boryl complex with CO occurs reductively, yielding further B-O bonds as well as CO gas.
View Article and Find Full Text PDFChemphyschem
November 2024
Department of Chemistry, School of Natural Sciences, The University of Manchester, Oxford Road, Manchester, M13 9PL, UK.
The actinide-actinide bonding in tri-actinide clusters [An₃Cl₆] (An=Ac-Pu, z=1-6) and [An₃Cl₆Cp₃] (z=-2-+3; Cp=(η-CH)) is studied using density functional theory. We find 3-centre bonding similar to the tri-thorium cluster [{Th(η⁸-C₈H₈)(μ₃-Cl)₂}₃{K(THF)₂}₂], as we previously reported (Nature 2021, 598, 72-75). The population of 3-centre molecular orbitals (3c-MOs) by zero, one or two electrons correlates with shortening of the An-An bond lengths, which also decrease with increasing actinide atomic number, consistent with the contraction of the actinide valence atomic orbitals.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
October 2024
Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC, V6T 1Z1, Canada.
Post-synthetic modification of mechanically interlocked molecules (MIMs) is an attractive avenue to add complexity to already intricate systems. This remains an important, challenging topic that is under-developed. In this paper, we report the synthesis and characterization of a [2]rotaxane molecule featuring a ring appended to an emissive cyclometalated Pt unit.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!