SUPPLEMENTARY DATA ON CHEMISTRY OF PHOSPHACYMANTRENE

We have systematically studied the acylation reaction of 3,4-dimethylphosphacymantrene 3 which yields the corresponding 2-acyl derivatives. The CO → CH2 reduction of these acyl derivatives is performend by AlCl3 + LiAlH4. The CO → CH(OH) conversion is performed by NaBH4. Various attempts to obtain the 2-carboxy acid derivative of 3 by degradative oxidation of the corresponding 2-acetyl derivative in basic medium have failed. However, the 2-carbethoxy-3,4-dimethylphosphacymantrene 12 has been obtained in low yield by reaction of the corresponding 1-phenylphosphole sulfide with Mn2(CO)10. The P → Fe(CO)4 complex of 3 has been prepared by reaction of 3 with Fe(CO)4 THF. Upon complexation the CP couplings within the ring disappear and a strong deshielding of the phosphorus atom is observed. © 1979.