The synthesis of terminal hydroxide containing Group 13 and 14 metals [LAl(OH)(2)], LAlMeOH, [{LAl(OH)}(2)(mu-O)], LAl(OH)-O-AlLL', LGeOH, and [TsiSn(O)OH](3) [Tsi = (Me(3)Si)(3)C] has been accomplished using innovative synthetic methodologies. All of these compounds have been structurally characterized, both in solution as well as in the solid state. The utility of such metal hydroxides [{LAl(OH)}(2)(mu-O)] and LAlMeOH [L = HC{(CMe)(2,6-i-Pr(2)C(6)H(3)N)}(2)] in the preparation of homo- and heterometallic compounds has been demonstrated. It has also been possible to prepare unusual terminal SH- and SeH-containing compounds LAl(SH)(2), LAl(SeH)(2), and LAl(SeH)-Se-Al(SeH)L using dihydride LAlH(2) as a starting material. The synthesis, structure, and potential utility of these compounds is discussed.