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Synthesis and X-ray crystal structure of the new palladium(I) dimer [Pd{sub 2}(PMe{sub 3}){sub 6}][hfac]{sub 2} and its conversion to [PdMe(PMe{sub 3}){sub 3}][hfac] via activation of phosphorous-carbon bonds

Journal Article · · Inorganic Chemistry
; ;  [1]
  1. Univ. of Illinois, Urbana, IL (United States)
Comproportionation of the palladium (O) compound Pd(PMe{sub 3}){sub 4} with the palladium(II) hexafluoroacetylacetonate compound Pd(hfac){sub 2} or [Pd(hfac)(PMe{sub 3}){sub 2}][hfac] gives the novel palladium(I) dimer [Pd{sub 2}(PMe{sub 3})]{sub 6}[hfac]{sub 2} (1). The analogous mixed-metal complex [PdPt(PMe{sub 3}){sub 6}][hfac]{sub 2} (2) can be prepared similarly. The {sup 1}H and {sup 31}PNMR spectra are consistent with structures in which the two metal centers are connected by a metal-metal bond and the six terminal PMe{sub 3} ligands complete two mutually perpendicular square-planar coordination environments; the hfac groups are not attached to the metal centers and instead serve as counterions for the [M{sub 2}(PMe{sub 3}){sub 6}]{sup 2+} cations. This structure has been established by X-ray crytsallography for the dipalladium(I) compound; the cation has 2-fold crystallographic symmetry, and the Pd-Pd distance is 2.598(1) {Angstrom}.
Sponsoring Organization:
USDOE
DOE Contract Number:
FG02-91ER45439
OSTI ID:
450859
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 10 Vol. 33; ISSN 0020-1669; ISSN INOCAJ
Country of Publication:
United States
Language:
English