Rational Syntheses and Serendipity: Complexes [LSnPtCl2(SMe2)]2, [{LSnPtCl(SMe2)}2SnCl2], [(LSn)3(PtCl2)(PtClSnCl){LSn(Cl)OH}], and [O(SnCl)2(SnL)2] with L=MeN(CH2CMe2O)2

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Syntheses and molecular structures of the dimeric tin–platinum complex [LSnPtCl2(SMe2)]2 (2), the tin–platinum clusters [{LSnPtCl(SMe2)}2SnCl2)] (3) and [(LSn)3(PtCl2)(PtClSnCl)(LSnOHCl)] (6) (L=MeN(CH2CMe2O−)2), and of the unprecedented tin(II) aminoalkoxide–tin oxide chloride complex [O(SnCl)2⋅(SnL)2] (5) are reported. The compounds were characterized by NMR spectroscopy (1H, 13C, 119Sn, 195Pt), 119Sn Mössbauer spectroscopy (1–3, 6), electrospray ionization mass spectrometry, elemental analyses, and single‐crystal X‐ray diffraction analyses (2⋅CH2Cl2, 3⋅2 C4H8O, 5, 6⋅3CH2Cl2). The tin(II) aminoalkoxide [MeN(CH2CMe2O)2Sn]2 (1) behaves like a neutral ligand, inserts into a Pt−Cl bond, or is involved in rearrangement reactions with the different behavior occurring even within one compound (3, 6). DFT calculations show that the tin–platinum compounds behave like electronic chameleons.