Stable “Inverse” Sandwich Complex with Unprecedented Organocalcium(I): Crystal Structures of [(thf)₂Mg(Br)-C₆H₂-2,4,6-Ph₃] and [(thf)₃Ca{μ-C₆H₃-1,3,5-Ph₃}Ca(thf)₃]

• Abstract
• Full Text HTML
• Hi-Res PDF[870 KB]
• PDF w/ Links[277 KB]

• Supporting Info
• Figures
• Citing Articles

Your current credentials do not allow retrieval of the full text.

Purchase the full-text

• PDF/HTML,
  figures/images,
  references and tables,
  (where available)

Abstract

The reaction of bromo-2,4,6-triphenylbenzene with activated magnesium in THF yielded the Grignard reagent [(thf)₂Mg(Br)-C₆H₂-2,4,6-Ph₃] (1) with a Mg−C bond length of 214.8(3) pm. A similar reaction of bromo-2,4,6-triphenylbenzene with activated calcium led to an “inverse” sandwich complex [(thf)₃Ca{μ-C₆H₃-1,3,5-Ph₃}Ca(thf)₃] (2) with the calcium atoms on opposite sides of the central arene ring showing small Ca−Ca′ and Ca−C distances of 427.9(3) and 259.2(3) pm. This extremely air- and moisture-sensitive complex exhibits thermochomic and solvatochromic behavior. It is paramagnetic with spin of S = 1 (triplet) with an ESR resonance at g = 2.0023. Quantum chemical calculations shed light on the bonding situation in this very unusual dinuclear Ca(I) compound.

Citing Articles

View all 10 citing articles

Citation data is made available by participants in CrossRef's Cited-by Linking service. For a more comprehensive list of citations to this article, users are encouraged to perform a search in SciFinder.

This article has been cited by 10 ACS Journal articles (5 most recent appear below).

• 

  Syntheses and Structures of Magnesium Complexes with Reduced α-Diimine Ligands

  Jing Gao, Yanyan Liu, Yanxia Zhao, Xiao-Juan Yang, and Yunxia Sui
  Organometallics2011 30 (22), 6071-6077

  • Syntheses and Structures of Magnesium Complexes with Reduced α-Diimine Ligands

    Jing Gao, Yanyan Liu, Yanxia Zhao, Xiao-Juan Yang, and Yunxia Sui
    Organometallics2011 30 (22), 6071-6077

    The reduction of neutral α-diimine ligands bearing different substituents on the N-aryl rings by different amounts of potassium metal and subsequent reaction with anhydrous MgCl2 in THF afforded a series of magnesium compounds, [(LiPr)2–Mg(THF)2]·THF (2), ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Synthesis and Structural Characterization of Alkaline-Earth-Metal Bis(amido)silane and Lithium Oxobis(aminolato)silane Complexes

  Dongming Yang, Yuqiang Ding, Haishun Wu, and Wenjun Zheng
  Inorganic Chemistry2011 Article ASAP

  • Synthesis and Structural Characterization of Alkaline-Earth-Metal Bis(amido)silane and Lithium Oxobis(aminolato)silane Complexes

    Dongming Yang, Yuqiang Ding, Haishun Wu, and Wenjun Zheng
    Inorganic Chemistry2011 Article ASAP

    Several of alkaline-earth-metal complexes [(η2:η2:μ(N):μ(N)-Li)+]2[{η2-Me2Si(DippN)2}2Mg]2– (4), [η2(N,N)-Me2Si(DippN)2Ca·3THF] (5), [η2(N,N)-Me2Si(DippN)2Sr·THF] (6), and [η2(N,N)-Me2Si(DippN)2Ba·4THF] (7) of a bulky bis(amido)silane ligand were readily ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Binuclear Alkaline Earth Metal Compounds (Be, Mg, Ca, Sr, Ba) with α-Diimine Ligands: A Computational Study

  Shaoguang Li, Xiao-Juan Yang, Yanyan Liu, Yanxia Zhao, Qian-Shu Li, Yaoming Xie, Henry F. Schaefer, and Biao Wu
  Organometallics2011 Article ASAP

  • Binuclear Alkaline Earth Metal Compounds (Be, Mg, Ca, Sr, Ba) with α-Diimine Ligands: A Computational Study

    Shaoguang Li, Xiao-Juan Yang, Yanyan Liu, Yanxia Zhao, Qian-Shu Li, Yaoming Xie, Henry F. Schaefer, and Biao Wu
    Organometallics2011 Article ASAP

    A series of dinuclear alkaline earth metal (Ae) structures Na2[(CHNH)2Ae–Ae(CHNH)2] (1–5) and (CHNH)2Ae–Ae(CHNH)2 (6–10) containing Ae–Ae bonds were optimized using density functional theory (DFT) and hybrid Hatree-Fock/DFT methods. The geometric and NBO ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Halide Coordination of Perhalocyclohexasilane Si₆X₁₂ (X = Cl or Br)

  Xuliang Dai, Seok-Bong Choi, Christopher W. Braun, Pooja Vaidya, Svetlana Kilina, Angel Ugrinov, Douglas L. Schulz, and Philip Boudjouk
  Inorganic Chemistry2011 Article ASAP

  • Halide Coordination of Perhalocyclohexasilane Si₆X₁₂ (X = Cl or Br)

    Xuliang Dai, Seok-Bong Choi, Christopher W. Braun, Pooja Vaidya, Svetlana Kilina, Angel Ugrinov, Douglas L. Schulz, and Philip Boudjouk
    Inorganic Chemistry2011 Article ASAP

    The addition of halide anions (X′ = Cl−, Br−, or I−) to perhalocyclohexasilane Si6X12 (X = Cl or Br) led to the formation of complexes comprising [Si6X12X′2]2− dianions. An upfield shift in the 29Si NMR spectra was noted upon coordination, and structural ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Calcium Complexes of Noninnocent α-Diimine Ligands

  Yanyan Liu, Yanxia Zhao, Xiao-Juan Yang, Shaoguang Li, Jing Gao, Peiju Yang, Yana Xia, and Biao Wu
  Organometallics2011 30 (6), 1599-1606

  • Calcium Complexes of Noninnocent α-Diimine Ligands

    Yanyan Liu, Yanxia Zhao, Xiao-Juan Yang, Shaoguang Li, Jing Gao, Peiju Yang, Yana Xia, and Biao Wu
    Organometallics2011 30 (6), 1599-1606

    A series of calcium compounds with α-diimine ligands, [L−Ca-(μ2-Cl)(THF)2]2 (1, L = LiPr; 2, L = LMes), [(LiPr)2−2CaK2(THF)]n (3), [(LMes)2−Na(THF)2]2Ca (4), and [Ca(LiPr)2−Li(THF)(μ3-Cl)Li(THF)2(μ3-Cl)]2 (5), where LiPr = [(2,6-iPr2C6H3)NC(Me)]2 and LMes ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links

SciFinder Links

• Get Reference Detail
• Get Substances
• Get Reactions
• Get Cited
• Get Citing