Résumé : The complex {[(CH3)2Sn]2[(CH3)2SnO](OCH3)(HONZO)(ONZO)} (3) [ONZOH is the oximate residue, o-(–ON=CH–C6H4–OH), HONZO the corresponding phenolate residue, o-(HON=CH–C6H4–O–), and ONZO the dibasic species o-(–ON=CH–C6H4–O–), all derived from salicylaldoxime, o-(HON=CH–C6H4–OH)] reacts with an excess of racemic (d,l)-2-methyl-1-butanol to afford the μ2-substitution product 5a {[(CH3)2Sn]2[(CH3)2SnO][OCH2CH(CH3)CH2CH3](HONZO)(ONZO)]}. Crystallographic characterisation of the trinuclear microcluster 5a shows the presence of the monobasic HONZO ligand in a tridentate μ2-O,N mode and of the dibasic ONZO ligand in a tridentate O,N,O mode. This coordination mode leads to one seven-coordinate and two five-coordinate tin centers that are linked by a μ3-oxo function. The coordination geometries are distorted pentagonal bipyramidal and trigonal bipyramidal, respectively. The two low-coordinate tin atoms are linked by the alkoxide ion. The corresponding chiral (S)-2-methyl-1-butanol reacts analogously to yield 5b. By contrast, reaction of 3 with chiral secondary alcohols (2-butanol or 1-phenyl-1-ethanol), in various molar ratios, failed to provide the corresponding μ2-alkoxy complex. Instead, pure crystals of {[(CH3)2Sn]2[(CH3)2SnO](OH)(HONZO)(ONZO)} (2a) were isolated.