Catalytic process for polyhydric alcohols and derivatives

A process for making alkane polyols which comprises reacting at a pressure of from about 500 psia to about 50,000 psia and a temperature of about 100.degree.C. to about 375.degree.C., a mixture consisting essentially of oxides of carbon and hydrogen in the presence of a bis(triorgano phosphine) iminium cation of the formula ##EQU9## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are alkyl, cycloalkyl, aryl, alkaryl, araalkyl, beta-hydroxyethyl, ethoxymethyl, ethoxylethyl, phenoxyethyl or a polyalkylene ether group of the formula C.sub.n H.sub.2n O).sub.x -OR wherein n has an average value from 1 to 4, x has an average value from 2 to about 150, and R may be hydrogen or alkyl of 1 to about 12 carbon atoms and a rhodium carbonyl complex, said complex is provided to the reaction as a rhodium carbonyl cluster which possesses an infrared spectrum which exhibits three intense wavelength bands between about plus and minus 10 cm.sup..sup.-1 of about 1868 cm.sup..sup.-1, about 1838 cm.sup..sup.-1, and about 1785 cm.sup..sup.-1, at a pressure of at least about 500 pounds per square inch absolute.