The syntheses are reported of the novel heteroleptic organostannylenes [2,6-(ROCH(2))(2)C(6)H(3)]SnCl (1, R = Me; 2, R = t-Bu) and of their tungstenpentacarbonyl complexes [2,6-(ROCH(2))(2)C(6)H(3)](X)SnW(CO)(5) (3, X = Cl, R = Me; 4, X = Cl, R = t-Bu; 5, X = H, R = Me). The compounds were characterized by means of elemental analyses, (1)H, (13)C, (119)Sn NMR spectroscopies, electrospray mass spectrometry and in case of 3 and 4 also by single crystal X-ray diffraction analysis. For the two latter compounds the substituents bound at the ether oxygen atom control the strength of intramolecular O -> Sn coordination. Thus, the O-Sn distances amount to 2.391(5)/2.389(5) (3) and 2.464(3)/2.513(3) angstrom (4). (C) 2008 Elsevier B.V. All rights reserved.