ZUR REAKTION VON METALL-KOORDINIERTEM KOHLENMONOXID MIT YLIDEN. XV. NEUARTIGE SPALTUNG VON KOHLENMONOXID VIA β-TRIMETHYLPHOSPHONIO(α-TRIMETHYLSILOXY)VINYL-KOMPLEXE: EINBAU DES CARBONYLKOHLENSTOFFS IN EINEN β-TRIMETHYLPHOSPHONIOACETYLID-LIGANDEN

Article abstract of DOI:10.1016/0022-328X(84)85017-2

The manganese complexes RC5H4Mn(CO)3 (R=H (1a), Me (1b) react with Me3P=CHSiMe3 only under photochemical conditions to yield the ylide complexes RC5H4(CO)2Mn-CH(SiMe3)PMe3 (2a,2b).Treatment of the phosphonium or lithium manganeseacylates R4P(Li) (R=Me, Et; R'=H, Me) (3a,3b,5) with Me3SiOSO2CF3 leads to the formation of the vinyl complexes MeC5H4(CO)2Mn^--C(OSiMe3)=C(R')-P⁺R3 (4a,4b).Pure 4a slowly eliminates Me3SiOH at room temperature to produce the β-trimethylphosphonio-acetylide complex MeC5H4(CO)2Mn^--C<*>C-P⁺Me3 (6).In the presence of a catalytic amount of Me3P=CH2 4a is rapidly cleaved to 1b and Me3P=CHSiMe3.