Low-Coordinate Chromium Siloxides: The "Box" [Cr(μ-OSitBu3)]4, Distorted Trigonal [(tBu3SiO)3Cr] [Na(benzene)] and [(tBu3SiO)3Cr] [Na(dibenzo-18-c-6)], and Trigonal (tBu3SiO)3Cr

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Article discussing low-coordinate chromium siloxides and the "box" [Cr(μ-Cl)(μ-OSiᵗBu₃)]₄, distorted trigonal [(ᵗBu₃SiO)₃Cr][Na(benzene)] and [(ᵗBu₃SiO)₃Cr][Na(dibenzo-18-c-6)], and trigonal (ᵗBu₃SiO)₃Cr.

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Sydora, Orson L.; Wolczanski, Peter T.; Lobkovsky, Emil B.; Buda, Corneliu & Cundari, Thomas R., 1964- March 24, 2005.

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Article discussing low-coordinate chromium siloxides and the "box" [Cr(μ-Cl)(μ-OSiᵗBu₃)]₄, distorted trigonal [(ᵗBu₃SiO)₃Cr][Na(benzene)] and [(ᵗBu₃SiO)₃Cr][Na(dibenzo-18-c-6)], and trigonal (ᵗBu₃SiO)₃Cr.

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Reprinted with permission from Inorganic Chemistry. Copyright 2005 American Chemical Society.

Abstract: Treatment of CrCl2(THF)2 with NaOSitBu3 afforded the tetrameric "box" [Cr(μ-OSitBu3)]4 (1,X-ray). THF cleaved 1 to provide trans-(silox)ClCr(THF)2 (2), whereas degradation of 1 with 4-picoline caused disproportionation and the generation of trans-Cl2Cr(4-pic)2 and trans-(silox)2 Cr(4-pic)x (n=2,3; 3,3-4-pic). Chromous centers in 1 were antiferromagnetically coupled, and density functional calculations on the high-spin (multiplicity = 17) model [Cr-(μ-Cl)(μ-OH)]4 (1') revealed that its singly occupied 3d orbitals spanned an energy range of ͠2 eV. The addition of 8 equiv of Na(silox) to 1 yielded [(tBu3SiO)Cr(μ-OSitBu3)2] Na·C6H6 (4, Y shaped, ∠OCrO(Na) = 91.28(7)°), and treatment of 4 with dibenzo-18-crown-6 produced [(silox)(3)Cr] [Na(dibenzo-18-crown-6)] (5, ∠OCrO = ͠120°, (120 + α)°, (120 - α)°). Calculations of [((t)Bu(3)SiO)Cr(mu-OSi(t)Bu(3))(2)]Na (4') and Cr(silox)(3)(-) (5') provided reasonable matches with the experimental geometries (X-ray). The trigonal chromic derivative (silox)(3)Cr(6) was synthesized from CrCI(3)(THF)(3) for structural and calculational comparisons to the chromous derivatives.

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  • Inorganic Chemistry, 2005, Washington DC: American Chemical Society, pp. 2606-2618

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  • Publication Title: Inorganic Chemistry
  • Volume: 44
  • Issue: 8
  • Page Start: 2606
  • Page End: 2618
  • Pages: 13
  • Peer Reviewed: Yes

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  • March 24, 2005

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  • Feb. 13, 2012, 2:23 p.m.

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Sydora, Orson L.; Wolczanski, Peter T.; Lobkovsky, Emil B.; Buda, Corneliu & Cundari, Thomas R., 1964-. Low-Coordinate Chromium Siloxides: The "Box" [Cr(μ-OSitBu3)]4, Distorted Trigonal [(tBu3SiO)3Cr] [Na(benzene)] and [(tBu3SiO)3Cr] [Na(dibenzo-18-c-6)], and Trigonal (tBu3SiO)3Cr, article, March 24, 2005; [Washington, DC]. (digital.library.unt.edu/ark:/67531/metadc75423/: accessed June 18, 2018), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.