In the present work the chemistry of group 14 and 13 element oxide hydroxides has been extended to a new series of well-defined stannoxanes, indoxanes and thalloxanes that are kinetically stabilized by a bulky m-terphenyl substituent. The controlled base hydrolysis of appropriate m-terphenyltin trichloride (1) and m terphenylindium dichloride (10) produced along with intermediate products, the trinuclear organostannonic acid [2,6-Mes2C6H3SnO(OH)]3 (3) and the tetranuclear indium dihydroxide

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... Mes2C6H3In(OH)2]4 (14). Whereas the exposure to air of a mixture of m terphenyl thallium and lithium chloride resulted in (2,6 Mes2C6H3Tl)2(μ OH)2Cl2 (26), base hydrolysis of which proceeded with partial cleavage of the m-terphenyl substituent and yielded the thalloxane cluster (2,6 Mes2C6H3Tl)4Tl2(μ3 O)4(μ OH)6 (27). In moist C6D6, 3 reversibly react with water to give the monomeric organostannonic acid 2,6-Mes2C6H3Sn(OH)3 (3a). The reaction of (tBu2SnO)3 with 3 proceeded with the absorption of atmospheric CO2 and give rise to the multinuclear hypercoordinated organostannoxane carbonate [tBu2Sn(OH)OSnR(OH)2OC(OSntBu2OH)2(O)SnR(OH)(H2O)]2 (R = 2,6 Mes2C6H3) (5). Whereas the treatment of (2,6-Mes2C6H3In)2(μ-Cl)2Cl2 (10) and 14 with (tBu2SnO)3 resulted in the synthesis of stannaindoxane clusters (2,6-Mes2C6H3In)(tBu2Sn)2O(OH)2Cl2 (18) and (2,6 Mes2C6H3In)2(tBu2Sn)O(OH)2 (19). Bubbling CO2 through a solution of 3 did not have any reaction however 14 reacted with CO2 to produce a bicarbonate cluster (2,6 Mes2C6H3In)3(HCO3)2(OH)4 (20) in chloroform and a carbonate cluster (2,6 Mes2C6H3In)4(CO3)2(OH)4(H2O)2 (21) in THF. The treatment of diphenylphosphinic acid with 3 resulted in [2,6 Mes2C6H3Sn(OH)2 (O2PPh2)]2 (8) whereas 14 reacted with diphenylphosphinic acid to produce [(2,6 Mes2C6H3In)2(OH)(O2PPh2)3] (16). 14 also reacted with Me2P(O)OH and Me5C3HP(O)OH resulting in the formation of novel multinuclear organoindoxane phosphinate clusters (2,6 Mes2C6H3In)2(OH)2(O2PMe2)2 (15) and (2,6 Mes2C6H3In) (Me5C3HPO)2(H2O)2 (17). The ve [...]