Structural Dichotomy in Six-Coordinate d⁰ Complexes: Trigonal Prismatic (ᵗBu₃SiC≡C)₆Ta⁻ and Octahedral (ᵗBu₃SiC≡C)₆M²⁻ (M = Zr, Hf)

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Article discussing structural dichotomy in six-coordinate d⁰ complexes and trigonal prismatic (ᵗBu₃SiC≡C)₆Ta⁻ and octahedral (ᵗBu₃SiC≡C)₆M²⁻ (M ≡ Zr, Hf).

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13 p.

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Vaid, Thomas P.; Veige, Adam S.; Lobkovsky, Emil B.; Glassey, Wingfield V.; Wolczanski, Peter T.; Liable-Sands, Louise M. et al. September 19, 1998.

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Article discussing structural dichotomy in six-coordinate d⁰ complexes and trigonal prismatic (ᵗBu₃SiC≡C)₆Ta⁻ and octahedral (ᵗBu₃SiC≡C)₆M²⁻ (M ≡ Zr, Hf).

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13 p.

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Reprinted with permission from the Journal of the American Chemical Society. Copyright 1998 American Chemical Society.

Abstract: Utilization of the bulky acetylide, ᵗBu₃SiC≡C⁻, enabled the synthesis of several early metal polyacetylides. Addition of NaC≡CH to ᵗBu₃SiBr in dimethyl sulfoxide afforded ᵗBu₃SiC≡CH, which was deprotonated to yield ᵗBu₃SiC≡CLi. Treatment of ZrCl₄, HfCl₄, adn TaCl₅ with varying amounts of ᵗBu₃SiC≡CLi gave {(THF)₂Li(ᵗBu₃SiC≡C)₂}Zr(C≡CSiᵗBu₃)₃(THF) (1; THF = tetrahydrofuran), {Et₂O)Li(ᵗBu₃SiC≡C)₂}Hf(C≡CSiᵗBu₃)₃(OEt₂) (2), {Li(ᵗBu₃SiC≡C)₃}₂M(M = Zr, 6; Hf, 7), and {Li(ᵗBu₃SiC≡C)₃}Ta(C≡CSiᵗBu₃)₃ (3). Metathesis of 3 with KOTf generated KTa(C≡CSiᵗBu₃)₆ (4) and cation sequestration of 4 with crypt 2.2.2 provided [K(crypt 2.2.2)][Ta(C≡CSiᵗBu₃)₆](5). Single-crystal X-ray structural studies determined the structures (core symmetry) of 1 (Oh), 2, (Oh), 3 (D₃), 5 (D₃), 6 (Oh), and 7 (Oh). The D₃h to D₃ twist in 3 and 5 has a steric origin, and the counterion position appears inconsequential. Origins of the structural preferences illustrated by the dichotomous twisted trigonal prismatic and octahedral cores of the d⁰ hexaacetylides 5 and 6 were probed through density functional (ADF) and effective core potential (GAMESS) calculations. The structural difference results from a lessening electronic preference for the trigonal prism-primarily a greater HOMO/LUMO gap-upon moving from Ta to Zr, minor steric factors, and increased interligand repulsions in the dianion (VSEPR).

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  • Journal of the American Chemical Society, 1998, Washington DC: American Chemical Society, pp. 10067-10079

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  • Publication Title: Journal of the American Chemical Society
  • Volume: 120
  • Issue: 39
  • Page Start: 10067
  • Page End: 10079
  • Peer Reviewed: Yes

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  • September 19, 1998

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  • Oct. 9, 2012, 10:02 a.m.

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Vaid, Thomas P.; Veige, Adam S.; Lobkovsky, Emil B.; Glassey, Wingfield V.; Wolczanski, Peter T.; Liable-Sands, Louise M. et al. Structural Dichotomy in Six-Coordinate d⁰ Complexes: Trigonal Prismatic (ᵗBu₃SiC≡C)₆Ta⁻ and Octahedral (ᵗBu₃SiC≡C)₆M²⁻ (M = Zr, Hf), article, September 19, 1998; [Washington, D.C.]. (digital.library.unt.edu/ark:/67531/metadc107797/: accessed July 27, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.