3-Center-4-Electron Bonding in [(silox)2Mo=NtBu]2(μ-Hg) Controls Reactivity while Frontier Orbitals Permit a Dimolybdenum π-Bond Energy Estimate

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Article describing research on 3-center-4-electron bonding in [(silox)2Mo=NtBu]2(mu-Hg).

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2 p.

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Rosenfeld, Devon C.; Wolczanski, Peter T.; Barakat, Khaldoon A.; Buda, Corneliu & Cundari, Thomas R., 1964- May 18, 2005.

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Article describing research on 3-center-4-electron bonding in [(silox)2Mo=NtBu]2(mu-Hg).

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2 p.

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Reprinted with permission from the Journal of the American Chemical Society. Copyright 2005 American Chemical Society.

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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  • Journal of the American Chemical Society, 2005, Washington DC: American Chemical Society, pp. 8262-8263

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  • Publication Title: Journal of the American Chemical Society
  • Volume: 127
  • Page Start: 8262
  • Page End: 8263
  • Pages: 2
  • Peer Reviewed: Yes

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  • May 18, 2005

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  • March 2, 2012, 11:47 a.m.

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  • May 12, 2014, 11:19 a.m.

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Rosenfeld, Devon C.; Wolczanski, Peter T.; Barakat, Khaldoon A.; Buda, Corneliu & Cundari, Thomas R., 1964-. 3-Center-4-Electron Bonding in [(silox)2Mo=NtBu]2(μ-Hg) Controls Reactivity while Frontier Orbitals Permit a Dimolybdenum π-Bond Energy Estimate, article, May 18, 2005; [Washington, DC]. (digital.library.unt.edu/ark:/67531/metadc77136/: accessed February 22, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.