128025-11-6Relevant articles and documents
Linkage Isomerism in Rhodium(I) Complexes of Mixed Anhydrides of Diphenylphosphinous and Acrylic Acids: Crystal and Molecular Structure of
Borowski, Andrzej F.,Iraqi, Ahmed,Cupertino, Domenico C.,Irvine, Derek J.,Cole-Hamilton, David J.,et al.
, p. 29 - 34 (1990)
Reactions of with mixed anhydrides Rh2PO2CCr=CR'R'' (R=R'=Me or CH=CHMe; R=H, R'=H, R''=Me; R=Me, R'=H, R''=Ph) gives complexes (n=1, R=R'=H, R''=Me or CH=CHMe; n=2, R=H, R'=R''=Me; R=Me, R'=H, R''=Ph; R=R'=H, R''=CH=CMe).For n=1, the mixed anhydride is bound to the metal via the phosphorus atom and the double bond, whilst for n=2 binding is through phosphorus alone.Treatment of with TlPF6 or AgSbF6 leads in all cases to complexes >Rh(PPh3)2(Ph2PO2CCr=CR'R'')>+ in which the mixed anhydrideis bound through the phosphorus atom and the carbonyl oxygen atom.Spectroscopic diagnostics for the various different bonding modes are discussed, whilst their occurrence is rationalised largely on steric grounds.The X-ray crystal structure of is described along with its curious fluxional behaviour.Crystals of this complex are monoclinic (space group P21/n), with a=19.54(4), b=13.250(4), c=11.425(1) Angstroem, β=91.66(2) deg, and Z=4.The structure was obtained from 3721 observed intensities measured on an automatic diffractometer and refined to an R value of 0.0358.The complex is distorted square planar about rhodium with the co-ordination sites being occupied by the two phosphorus atoms, the chloride, and the C=C of the mixed anhydride.The two phosphorus atoms are mutually cis.The C=C bond length is 1.393(9) Angstroem, and there is significant pyramidalisation at the carbon atoms of the double bond, suggesting a fairly strong interaction between the double bond and the rhodium atom.
