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Volumn 125, Issue 45, 2003, Pages 13644-13645

Distinct Thermodynamics for the Formation and Cleavage of N-H Bonds in Aniline and Ammonia. Directly-Observed Reductive Elimination of Ammonia from an Isolated Amido Hydride Complex

Author keywords

[No Author keywords available]

Indexed keywords

AMIDE; AMMONIA; ANILINE; IRIDIUM COMPLEX;

EID: 0242659048     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja037363u     Document Type: Article
Times cited : (126)

References (22)
  • 10
    • 0035972367 scopus 로고    scopus 로고
    • For a theroetical treatment, see: (a) Macgregor, S. A. Organometallics 2001, 20, 1860.
    • (2001) Organometallics , vol.20 , pp. 1860
    • Macgregor, S.A.1
  • 20
    • 0242478290 scopus 로고    scopus 로고
    • note
    • In principle, formation of la instead of the analogue of ammonia complex 2 containing a coordinated arylamine could result from kinetic, rather than thermodynamic, effects, and the aniline analogue of 2 could be more stable than anilide hydride la. However, formation of Lewis acid-base complexes is typically fast; we therefore expect that the aniline analogue of 2 should be kinetically accessible, particularly at temperatures at which la undergoes rapid exchange with anilines. Attempts to prepare the aniline analogue of 2 at -35 °C gave a major product that appears to result from the coordination of aniline and cyclometalation of the aniline phenyl group. Upon warming to room temperature, the complex undergoes conversion to 1a. This preliminary observation is consistent with the expectation that coordination of the aniline nitrogen lone pair is kinetically facile.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.