Practical alternative procedures are described for the syntheses of octavinylsilsesquioxane 1, octaphenylsilesquioxane and octabenzylsilsesquioxane. The hydrolytic polycondensation of RSiX3 (R = CH2=CH-, C6H5- or C6H5CH2-; X = Cl, OCH3, or OC2H5) in the presence of solid acid or base Amberlite ion-exchange resin gave improved yields of the corresponding octameric oligosilsesquioxanes. Repetitive usage of the Amberlite resin as the hydrolysis reagent was tested during synthesis of 1. The results indicate that it could be used many times in the same solvent making the procedure a more economically viable technique.

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The o‐substituted hybrid phenylphosphines, PPh2(o‐C6H4NH2) and PPh2(o‐C6H4OH), could be deprotonated with LDA or n‐BuLi to yield PPh2(o‐C6H4NHLi) and PPh2(o‐C6H4OLi), respectively. When added to a solution of (η5‐C5H5)Fe(CO)2I at room temperature, these two lithiated reagents produce a chelated neutral complex 1 (η5‐C5H5)Fe(CO)[C(O)NH(o‐C6H4)PPh2‐C,P‐η2] for the former and mainly a zwitterionic complex 2, (η5‐C5H5)Fe+(CO)2[PPh2(o‐C6H4O−)] for the latter. Complex 1 could easily be protonated and then decarbonylated to give 4 [(η5‐C5H5)Fe(CO){NH2(o‐C6H4)PPh2‐N,P‐η2}+]. Complexes 1 and 4‐I have been crystallographically characterized with X‐ray diffraction.

Unable to elaborate (η5‐C5H5)Fe(CO)2C(O)Ph by the nucleophile/electrophile sequences, the treatment of nucleophile PhLi followed by Lewis base 2,2′‐bipyridine instead leads to the meaningful isolation of [(η5‐C5H5)Fe(CO) {C(O)Ph}2]2Li2(2,2′‐bipyridine).