Pt- and Pd-catalyzed reactions of a set of allyloxyaromatic mono- and diesters with selected silanes were examined to develop simple, mild methods of forming liquid crystal (LC)/siloxane and LC/silsesquioxane polymers. Pt complexes catalyze hydrosilylation to give primarily (less than or equal to 80% selectivity at 100% conversion) terminal silylation of the allyloxys. The catalyst, platinum-1,3-divinyltetramethyldisiloxane [Pt(dvs)], gives the cleanest reactions, fewest side products, under the mildest conditions. Model studies of Pt(dvs) catalyzed hydrosilylation of 4-allyloxy methylbenzoate gave relative reactivities (HSiO1.5)(8) much greater than Et(3)SiH > HMe(2)Si-O-SiMe(2)H > Ph(2)SiH(2). The cubic silsesquioxane, (HSiO1.5)(8), is so reactive hydrosilylation is over in 1-3 h at 0 degrees C. All other reactions required > 40 degrees C and longer reaction times. Initial efforts to form high polymers by Pt-catalyzed reactions of bis-allyloxy aromatics with Ph(2)SiH(2) provide polymers with bimodal MW distributions (polystyrene), M(w)s approximate to 30 kDa, and PDIs approximate to 5. Pd catalysis gives quite different products resulting from loss of propene with coincident formation of Si-O bonds, "oxysilylation." The same products appear (10-15%) in some Pt catalyzed reactions. Palladium dibenzylideneacetone/Ph(3)P [Pd(dba)(2)/Ph(3)P], gives the cleanest oxysilylation reactions. Relative oxysilylation activities are : Ph(2)SiH(2) > HMe(2)SiOSiMe(2)H > Et(3)SiH. Polymerization with Pd catalysts provides polymers with M(w)s approximate to 11 kDa, and PDIs approximate to 2. Reaction of 1 equiv. of (HSiO1.5)(8) with 4 equiv. of 4-( 4-allyloxy-benzoyloxy)biphenyl gives relatively pure tetrasubstituted LC/silsesquioxane [M(n) approximate to 1860 Da, PDI approximate to 1.09 (styrene equiv.) vs. 1746 Da calcd.]. A detailed analysis of the products formed, the catalytic reactivity patterns of the bis(allyloxy) aromatic diesters and their LC transitions is presented.