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Updated: Jul 9, 2026

Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry
Published on: October 18, 2019
3-center-4-electron bonding in [(silox)2Mo=NtBu]2(mu-Hg) controls reactivity while frontier orbitals permit a
Devon C Rosenfeld1, Peter T Wolczanski, Khaldoon A Barakat
1Department of Chemistry & Chemical Biology, Baker Laboratory, Cornell University, Ithaca, NY 14853, USA.
Abstract:
Na/Hg reduction of (silox)2Cl2Mo=NtBu (3) afforded C2h [(silox)2Mo=NtBu]2(mu-Hg) (12-Hg), which consists of two distorted trigonal monoprisms with Hg at the each apex (d(MoHg) = 2.6810(5) A). Calculations reveal 3c4e bonding in the linear MoHgMo linkage that renders 12-Hg susceptible to nucleophilic cleavage. Exposure to PMe3 and pyridine rapidly (<5 min) affords (silox)2(tBuN)MoLn (L = PMe3, n = 1 (1-PMe3); py, n = 2 (1-py2)), while poorer nucleophiles (L = C2H4, 2-butyne) yield adducts (e.g., 1-C2H4 and 1-C2Me2) after prolonged heating. The HOMO and LUMO of 12-Hg are "stretched" pi and pi* orbitals from which four states arise: 1Ag (GS), 3Bu, 1Bu, and 1Ag. DeltaE = E(1Bu) - E(3Bu) = 2K, where K is the exchange energy. Magnetic studies indicate E(3Bu) - E(1Ag) approximately 550 cm-1 (calcd 1744 cm-1), and a UV-vis absorption at 10 000 cm-1 is assigned to 1Ag --> 1Bu, permitting K to be evaluated as 4725 cm-1. With the pi --> pi* transition in Schrock's [Mo(NAr)(CH2tBu)(OC6F5)]2 (4) assigned at 528 nm, this estimation places its pi-bond energy as {E(pi2 --> pi1pi*1 in 4) - E(1Ag --> 1Bu in 12-Hg)} + E(1Ag --> 3Bu in 12-Hg) = 27 kcal/mol.
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