Adduct Studies and Reactivity of <i>trans</i>-[(C<sub>2</sub>F<sub>5</sub>)<sub>2</sub>MeP]<sub>2</sub>Pt(Me)X (X = O<sub>2</sub>CCF<sub>3</sub>, OTF, OSO<sub>2</sub>F)
作者:Jeffrey L. Butikofer、Thomas G. Parson、Dean M. Roddick
DOI:10.1021/om060847p
日期:2006.12.1
The comparative reactivity properties of previously reported trans-(dfmp)(2)Pt(Me)X (dfmp = (C2F5)(2)-MeP; X = O2CCF3, OTf, OSO2F) with small molecules are presented. Anionic ligand displacement by CO depends upon X and the corresponding acid solvent. In trifluoroacetic acid, treatment of trans(dfmp)(2)Pt(Me)(O2CCF3) with CO results in loss of dfmp to form the mixed phosphine/carbonyl product (dfmp)(CO)Pt(Me)(O2CCF3). However, in triflic and fluorosulfonic acids trans-(dfmp)(2)Pt(Me)(X) compounds react with CO to form trans-(dfmp)(2)Pt(Me)(CO)(+)(X)(-). trans-(dfmp)(2)Pt(Me)(X) systems react with H-2 under both acidic and aprotic conditions to form trans-(dfmp)(2)Pt(H)(X); trans-(dfmp)(2)Pt(H)(OTf) has been crystallographically characterized. Treatment of trans-(dfmp)(2)Pt(H)(OTf) with CO or dfmp gives trans-(dfmp)(2)Pt(H)(CO)(+) or (dfmp)(3)Pt(H)(+), respectively. In contrast to trans-(dfmp)(2)Pt(Me)(OTf), which releases methane in HOTf, trans-(dfmp)(2)Pt(Me)(OSO2F) in FSO3H at 80 degrees C cleanly produces the reductive elimination product MeOSO2F. Carbonylation of trans-[(dfmp)(2)PtMe(CO)]X-+(-) under 1000 psi CO in turn cleanly produces MeC(O)X at ambient temperatures. The mechanism of reductive elimination from these Pt(II) precursors is discussed.