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Volumn 48, Issue 43, 2009, Pages 8141-8145

Snapshots of the Al-Al σ-bond formation starting from {AlR 2} units: Experimental and computational observations

Author keywords

Aluminum; Aluminum phosphanides; Metal metal interactions; Radicals; Subvalent compounds

Indexed keywords

BOND FORMATION; METAL-METAL INTERACTIONS; QUANTUM CHEMICAL CALCULATIONS; RADICALS; SUBVALENT COMPOUNDS; UNPAIRED ELECTRONS;

EID: 70349974738     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200901754     Document Type: Article
Times cited : (69)

References (78)
  • 3
    • 70349957789 scopus 로고    scopus 로고
    • [6] species, there has been no evidence to date for monomeric radicals.
    • [6] species, there has been no evidence to date for monomeric radicals.
  • 8
    • 70349973328 scopus 로고    scopus 로고
    • 2Al-bridged bonding) were to be trapped.
    • 2Al-bridged bonding) were to be trapped.
  • 12
    • 70349954674 scopus 로고    scopus 로고
    • Complex Math Equation
    • Complex Math Equation
  • 14
    • 70349973330 scopus 로고    scopus 로고
    • At the same time, an amorphous colorless solid is formed that makes the separation of the green crystals challenging.
    • At the same time, an amorphous colorless solid is formed that makes the separation of the green crystals challenging.
  • 16
    • 70349961375 scopus 로고    scopus 로고
    • The computational results, also employing further functionals and basis sets, are reported in great detail in Ref. [9]. Even shorter Al-Al distances are calculated with other functionals.
    • The computational results, also employing further functionals and basis sets, are reported in great detail in Ref. [9]. Even shorter Al-Al distances are calculated with other functionals.
  • 22
    • 70349959778 scopus 로고    scopus 로고
    • [17]
    • [17]
  • 25
    • 70349973342 scopus 로고    scopus 로고
    • 3 is formed under these conditions by continuous dispro-portionation and precipitation of solid Al.
    • 3 is formed under these conditions by continuous dispro-portionation and precipitation of solid Al.
  • 27
    • 70349928538 scopus 로고    scopus 로고
    • [21]
    • [21]
  • 28
    • 70349967580 scopus 로고    scopus 로고
    • The elongation of an existing Al-Al s bond (e.g. in 5) and subsequent formation of compound 1 is not possible from a thermodynamic point of view.
    • The elongation of an existing Al-Al s bond (e.g. in 5) and subsequent formation of compound 1 is not possible from a thermodynamic point of view.
  • 29
    • 70349939275 scopus 로고    scopus 로고
    • [26]
    • [26] These authors attribute the Ga-H bond formation to hydrogen abstraction from the solvent by radical intermediates under their drastic reaction conditions.
  • 35
    • 70349975489 scopus 로고    scopus 로고
    • [9]
    • [9]
  • 55
    • 70349971276 scopus 로고    scopus 로고
    • The above-mentioned difficulties in the synthesis and isolation of 1 and its low stability at room temperature even in crystalline form did not allow for a definite experimental determination of the triplet state by ESR and SQUID measurements. Analyses of 1 in solution are less promising, as dissolving the crystals does not restore the green color of the solution the crystals were originally obtained from. Apparently, compound 1 is only formed in stationary low concentrations within the reaction solution according to Equation (1) and is immediately stabilized by the crystallization process. This process seems to circumvent a spin flip and the thermodynamically favored formation of compound 2.
    • The above-mentioned difficulties in the synthesis and isolation of 1 and its low stability at room temperature even in crystalline form did not allow for a definite experimental determination of the triplet state by ESR and SQUID measurements. Analyses of 1 in solution are less promising, as dissolving the crystals does not restore the green color of the solution the crystals were originally obtained from. Apparently, compound 1 is only formed in stationary low concentrations within the reaction solution according to Equation (1) and is immediately stabilized by the crystallization process. This process seems to circumvent a spin flip and the thermodynamically favored formation of compound 2.
  • 56
    • 70349956368 scopus 로고    scopus 로고
    • a development of University of Karlsruhe (TH) and Forschungszentrum Karlsruhe GmbH, 1989-2007, TURBOMOLE GmbH since 2007
    • a) TURBOMOLE V5.9 V6.0 2006-2009, a development of University of Karlsruhe (TH) and Forschungszentrum Karlsruhe GmbH, 1989-2007, TURBOMOLE GmbH since 2007; http://www.turbomole.com
    • TURBOMOLE V5.9 V6.0 2006-2009
  • 62
    • 70349973340 scopus 로고    scopus 로고
    • Erratum
    • Erratum
  • 78
    • 70349957890 scopus 로고    scopus 로고
    • PhD Thesis University of Karlsruhe (TH)
    • M. Kattannek, PhD Thesis 2006, University of Karlsruhe (TH)
    • (2006)
    • Kattannek, M.1


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.