Treatment of Mo(CO)(6) with cis,cis-1,3,5-tris(diphenylphosphino)-1,3,5-tris(methoxycarbonyl)cyclohexane (tdp-pcyme) (L) at elevated temperatures gives Mo(CO)(3)(tdppcyme) (1) in high yield. The ester groups in complex 1 are saponed to carboxylic acid groups by lithium n-propyl mercaptide in DMF and reduced to alcoholic groups by lithium aluminum hydride in THF to yield the carboxylic acid complex 2 and hydroxymethyl complex 4, respectively. Treatment of 1 with ethylenediamine and NaH results in the formation of the carboxamide 3. The methoxymethyl complex 5 is formed from 4 in a phase transfer reaction (THF/aqueous NaOH) with dimethyl sulfate as the methylating agent. Deprotonation of compound 4 with NaH in THF results in the formation of the corresponding trisodium alcoholate which on treatment with chloromethyl methyl ether, 1-methoxy-2-[p-tolylsulfonyl)oxy]ethane, and allyl bromide leads to the corresponding complexes 6-8, respectively. The acid catalyzed addition of the hydroxyl function to 5,6-dihydro-4H-pyran yields the acetal 9. The modified functionalized tripodal phosphines 2a and 5a-9a can be liberated by irradiating solutions of the corresponding molybdenum carbonyl complexes in the presence of pyridine N-oxide or N2O, respectively. No oxidation of the phosphines is observed; MoO3 and CO are obtained. Single-crystal X-ray structure determinations were performed on complexes 3 and 5.