Comparison of MgYb and Mg-Ca bonding: structures, electronic analyses and reactivities.
- 1Inorganic and Organometallic Chemistry, Universität Erlangen-Nürnberg Egerlandstrasse 1 Erlangen 91058 Germany [email protected].
- 2Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Facultat de Ciències, Universitat de Girona (UdG) C/Maria Aurèlia Capmany 69 Girona 17003 Catalonia Spain.
- 3Eenheid Algemene Chemie (ALGC), Vrije Universiteit Brussel (VUB) Brussels 1050 Belgium.
Abstract
Reaction of [(BDI*)MgNa]₂ with (Am*YbI)₂ in methylcyclohexane led to the precipitation of NaI and quantitative formation of (BDI*)Mg-Yb(Am*) (1-Yb); BDI* = HC[C(tBu)N(DIPeP)]₂, DIPeP = 2,6-Et₂CH-phenyl; Am* = tBuC(N-DIPP)₂, DIPP = 2,6-iPr-phenyl. Complex 1-Yb features a long unsupported 2c-2e Mg-Yb bond of 3.302 Å and crystallizes isomorphous to (BDI*)Mg-Ca(Am*) (1-Ca). The formal Mg⁰-YbII oxidation states in 1-Yb are confirmed by effective-oxidation-state analysis but the low reliability index of 68.0% indicates that this description is not fully representative of the electron distribution. Analysis of the electron density shows significant Mg⁰ → YbII electron transfer and therefore the complex has partial MgI-YbI character. EDA-NOCV analysis suggests that bonding in 1-Yb is best pictured as a combination of neutral open-shell radicals (BDI*)Mg˙/(Am*)Yb˙. Accordingly, (BDI*)Mg acts as an X-type ligand for Yb(Am*). The long, polarized Mg δ--Yb δ+ bond in 1-Yb is highly reactive. The thermal decomposition and reactivity of 1-Yb with N₂O, NH₃, 1,1-diphenylethylene, trans-stilbene and anthracene have been studied. Comparison with the reactivity of 1-Ca shows strong similarities, but also important differences. Most reactants oxidize the Mg⁰ centre in 1-Yb and 1-Ca and produce similar complexes that generally crystallize isomorphous. However, N₂O can also oxidize the YbII centre, resulting in paramagnetic YbIII products. In all cases, the Mg-Yb and Mg-Ca bonds in 1-Yb and 1-Ca are considerably more reactive than the unpolarized Mg-Mg bond in complexes of type (BDI)Mg-Mg(BDI).
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BibTeX
@article{thakur2026comparison,
title = {{Comparison of MgYb and Mg-Ca bonding: structures, electronic analyses and reactivities.}},
author = {Sandeep Kumar Thakur and Tanuja Tewari and Nil Roig and Jens Langer and Mercedes Alonso and Sjoerd Harder},
journal = {Chemical science},
year = {2026},
month = sep,
doi = {10.1039/d6sc05592c},
url = {https://europepmc.org/article/MED/42835594},
note = {CC BY},
}
RIS
TY - JOUR
TI - Comparison of MgYb and Mg-Ca bonding: structures, electronic analyses and reactivities.
AU - Sandeep Kumar Thakur
AU - Tanuja Tewari
AU - Nil Roig
AU - Jens Langer
AU - Mercedes Alonso
AU - Sjoerd Harder
PY - 2026
DA - 2026/09/21
JO - Chemical science
DO - 10.1039/d6sc05592c
UR - https://europepmc.org/article/MED/42835594
AB - Reaction of [(BDI*)MgNa]₂ with (Am*YbI)₂ in methylcyclohexane led to the precipitation of NaI and quantitative formation of (BDI*)Mg-Yb(Am*) (1-Yb); BDI* = HC[C(tBu)N(DIPeP)]₂, DIPeP = 2,6-Et₂CH-phenyl; Am* = tBuC(N-DIPP)₂, DIPP = 2,6-iPr-phenyl. Complex 1-Yb features a long unsupported 2c-2e Mg-Yb bond of 3.302 Å and crystallizes isomorphous to (BDI*)Mg-Ca(Am*) (1-Ca). The formal Mg⁰-YbII oxidation states in 1-Yb are confirmed by effective-oxidation-state analysis but the low reliability index of 68.0% indicates that this description is not fully representative of the electron distribution. Analysis of the electron density shows significant Mg⁰ → YbII electron transfer and therefore the complex has partial MgI-YbI character. EDA-NOCV analysis suggests that bonding in 1-Yb is best pictured as a combination of neutral open-shell radicals (BDI*)Mg˙/(Am*)Yb˙. Accordingly, (BDI*)Mg acts as an X-type ligand for Yb(Am*). The long, polarized Mg δ--Yb δ+ bond in 1-Yb is highly reactive. The thermal decomposition and reactivity of 1-Yb with N₂O, NH₃, 1,1-diphenylethylene, trans-stilbene and anthracene have been studied. Comparison with the reactivity of 1-Ca shows strong similarities, but also important differences. Most reactants oxidize the Mg⁰ centre in 1-Yb and 1-Ca and produce similar complexes that generally crystallize isomorphous. However, N₂O can also oxidize the YbII centre, resulting in paramagnetic YbIII products. In all cases, the Mg-Yb and Mg-Ca bonds in 1-Yb and 1-Ca are considerably more reactive than the unpolarized Mg-Mg bond in complexes of type (BDI)Mg-Mg(BDI).
SN - 2041-6520
SN - 2041-6539
ER -