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These compounds were obtained by addition of SnX<jats:sub>2<\/jats:sub> to the corresponding ligand inducing autoionization of the respective tin(II) halide. The thermal stability of <jats:bold>1<\/jats:bold>, <jats:bold>3<\/jats:bold>, and <jats:bold>4<\/jats:bold> was elucidated, giving, under ester cleavage and cyclisation, the tin(II) derivatives <jats:bold>8<\/jats:bold>\u2013<jats:bold>12<\/jats:bold>. The reaction of [L<jats:sup>1<\/jats:sup>SnCl]SnCl<jats:sub>3<\/jats:sub> (<jats:bold>1<\/jats:bold>) with W(CO)<jats:sub>4<\/jats:sub>(thf)<jats:sub>2<\/jats:sub> afforded the tungsten tetracarbonyl complex [{L<jats:sup>1<\/jats:sup>SnCl}{SnCl<jats:sub>3<\/jats:sub>}W(CO)<jats:sub>4<\/jats:sub>] (<jats:bold>13<\/jats:bold>), representing the first example in which a tin(II) stannate anion and a tin(II) stannylium cation simultaneously coordinate to a transition metal centre. The compounds were characterized by single crystal X\u2010ray diffraction analyses and in part by elemental analyses, IR and NMR spectroscopy, electrospray ionization mass spectrometry. 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