Processes are provided for producing organchlorosilanes and dipodal silanes in which an organic halide or alkene or chloralkene is reacted with a hydridochlorosilane in the presence of a quaternary phosphonium salt catalyst by providing sufficient heat to effect a dehydrohalogenative coupling reaction and/or a hydrosilylation reaction and venting the reaction to control reaction pressure and to remove gaseous byproducts from the reaction. The processes are preferably continuous using a catalyst in fluid form at reaction pressures not exceeding about 600 psi. The reactions may be carried out substantially isothermally and/or isobarically, for example in a plug flow reactor or continuous stirred tank reactor. The processes may produce novel silylated compounds including 1,2-bis (trichlorosilyl)decane or 1,2-bis (trimethoxysilyl)decane.