Trans-cis isomerization and structure of dimeric [Me2M-μ-N(H)NPh2]2 (M=Al, Ga)

Dongwon Cho, Jae E. Park, Byoung Jae Bae, Kwangyeol Lee, Bongsoo Kim, Joon T. Park

Research output: Contribution to journalArticlepeer-review

29 Citations (Scopus)

Abstract

Reaction of MMe3 (M=Al, Ga) with one equivalent of NH2NPh2 affords a dimeric complex [Me2M-μ-N(H)NPh2]2 [M=Al (1), M=Ga (2)] as a mixture of trans and cis isomers. Purification of 1 and 2 by recrystallization gives only trans isomers 1a and 2a, respectively. Variable-temperature 1H-NMR studies reveal that both 1 and 2 in solution undergo trans→cis isomerization with free energy of activation (ΔGc) values of 15.9 for 1 and 18.3 kcal mol-1 for 2. The solid state structures of trans isomers 1a and 2a have been determined by single-crystal X-ray diffraction studies. The molecular geometries of 1a and 2a consist of a centrosymmetric and dimeric unit (M-N)2 with two bridging hydrazido groups and two terminal methyl groups bound to each metal atom. The two N-NPh2 groups are trans to each other with respect to the (M-N)2 core plane. The coordination geometry of both metal and nitrogen atoms are distorted tetrahedral.

Original languageEnglish
Pages (from-to)162-167
Number of pages6
JournalJournal of Organometallic Chemistry
Volume592
Issue number2
DOIs
Publication statusPublished - 1999 Dec 25
Externally publishedYes

Keywords

  • 1,1-Diphenylhydrazine
  • Dimeric
  • Hydrazidoalane
  • Hydrazidogallane
  • Precursor

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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