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Low-valent Isocyanide Complexes and Clusters of Palladium and Platinum. Crystal Structure of (RNC)2> (R=2,6-Me2C6H3)
Yamamoto, Yasuhiro,Yamazaki, Hiroshi
, p. 2161 - 2166 (2007/10/02)
Reduction of (R=2,6-Me2C6H3) with sodium amalgam in the presence of isocyanide gave two clusters, (1a) and (2a), and two metallocycles, (RNC)2> (3a) and (RNC)2> (4a).In (2a) the six Pt atoms define a trigonal prism whose edges are associated with bridging and terminal isocyanide groups and the mercury atom is sanwiched by the two triangular Pt3 cores.The structure of (4a) was determined by X-ray analysis: space group Pbcn, a=18.542(11), b=22.702(5), c=22.197(5) Angstroem, and Z=8.In a similar reaction of (M=Pt or Pd) having bulky R groups 2,4-But2-6-MeC6H2 or 2,4,6-But3C6H2 gave the corresponding triangular trimetallic complexes .Six isocyanide molecules are bound to the metals as terminal and bridging ligands in the 2,4-di-t-butyl-6-methylphenyl isocyanide complex, and as only terminal isocyanide ligand in the 2,4,6-tri-t-butylphenyl isocyanide.Emission spectra of (2a) and the triangular palladium complexes were measured at 77 K; the former showed a fluorescence band at ca. 720 nm and the latter a phosphorescence band at ca. 640 nm.
