Asymmetrically Bonded π-Ligands. II. Hinging towards Metal of Substituted Allyls: Synthesis of Three 1-syn-EtOOCC3H4 Complexes and the Molecular Structure of[(η-1-EtOOCC3H4)Pd(tmeda)]BF4 (tmeda=N,N,N',N',-etramethylethylenediamine) at 185K and of [(η-1-EtOOCC3H4)PdCl]2 at 291K

David P. Grant*, Nicholas W. Murrall, Alan J. Welch

*Corresponding author for this work

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12 Citations (Scopus)

Abstract

The 4-, 5- and 6-coordinate complexes [(η-1-EtOOCC3H4)Pd(tmeda)]BF4, [(η-1-EtOOCC3H4)Pd(η-C5H5)] and [(η-1-EtOOCC3H4)RuCl(η-C6H6)] have been prepared and characterised, and a crystallographic study of the first undertaken. Crystals are triclinic, Pbar1, with two ion pairs in a cell of dimensions a 7.3076(23), b 8.0643(23), c 15.632(4) Å, α 89.255(22), β 78.834(22) and γ 76.812(20)° at 185 K. Using 4429 observed data the structure has been refined to R = 0.0452, and reveals asymmetry in the Pd-allyl bonding such that the substituted carbon atom is nearer to the metal, Pd-C(1) 2.124(4) Å, than is the unsubstituted allyl terminus, Pd-C(3) 2.131(4) Å. To emphasize the significance of this unusual result the structure of the dimeric precursor [(η-1-EtOOCC3H4)PdCl]2 has been determined. At 291 K one molecule of the dimer crystallises in space group Pbar1 in a cell of dimensions a 4.9800(18), b 6.174(3), c 14.080(3) Å, α 86.25(3), β 80.84(3) and γ 89.44(4)° (Ci symmetry imposed). The model has been refined to R = 0.0499 for 2239 observed data. In the dimer Pd-C(1) is 2.100(7), Pd-C(3) 2.131(8) Å.

Original languageEnglish
Pages (from-to)403-414
Number of pages12
JournalJournal of Organometallic Chemistry
Volume333
Issue number3
DOIs
Publication statusPublished - 27 Oct 1987

ASJC Scopus subject areas

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

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