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Synthesis and crystal structure of the novel platinum-bridged hexaruthenium alkynyl cluster Pt(Ru sub 3 (. mu. -H) l brace. mu. sub 4 -. eta. sup 2 -C triple bond (t-Bu) r brace (CO) sub 9 ) sub 2 : Evidence for the racemization of the chiral metal framework

Journal Article · · Organometallics; (USA)
DOI:https://doi.org/10.1021/om00115a016· OSTI ID:6614738
 [1]
  1. The University, Glasgow (Scotland)
The cluster Ru{sub 3}Pt({mu}-H){l brace}{mu}{sub 4}-{eta}{sup 2}-C{triple bond}C(t-Bu){r brace}(CO){sub 9}(COD) decomposes in dichloromethane or toluene solution by elimination of a Pt atom and COD, affording orange crystals of the title complex Pt(Ru{sub 3}({mu}-H){l brace}{mu}{sub 4}-{eta}{sup 2}-C{triple bond}C(t-Bu){r brace}(CO){sub 9}){sub 2} (5) in 40-50% yield. Crystal data for 5: triclinic, space group P{bar 1}; a = 9.546 (2), b = 12.993 (2), c = 17.786 (2) {angstrom}; {alpha} = 72.97 (1), {beta} = 82.48 (1), {gamma} = 74.62 (2){degree}; V = 2030.4 (6) {angstrom}{sup 3}; Z = 2; final R (R{sub w}) values 0.033 (0.038) for 4,806 independent observed (I > 3.0{sigma}(I)) data. Complex 5 contains two Ru{sub 3} cluster units linked by a naked Pt atom, with each cluster unit bonded via one Ru atom and the {alpha}-carbon of the alkynyl ligand. Variable-temperature {sup 13}C NMR spectra show that the chiral metal framework undergoes racemization with an estimated {Delta}G{sup {double dagger}}{sub 266} of 57.1 ({plus minus}1.1) kJ mol{sup {minus}1}.
OSTI ID:
6614738
Journal Information:
Organometallics; (USA), Journal Name: Organometallics; (USA) Vol. 9:1; ISSN 0276-7333; ISSN ORGND
Country of Publication:
United States
Language:
English