Reactivity of Organotin(I) Dimers RSnSnR (R = 2,6-(Me₂NCH₂)₂C₆H₃, 4‑<i>t</i>‑Bu-2,6-{P(O)(O‑<i>i</i>‑Pr)₂}₂C₆H₂) with Diaryl Dichalcogenides, ArEEAr (E = S, Se, Te; Ar = Ph, 2‑C₅H₄N): Control of Secondary Sn···Sn Interactions by Intramolecular Coordination and Identity of the Aryl Chalcogenate

The reactions of the in situ prepared organotin­(I) compounds RSnSnR with diaryl dichalcogenides ArEEAr provided, depending on the ratio of the reactants, the intramolecularly coordinated heteroleptic organotin­(II) chalcogenoarylates RSnEAr (<b>1</b>, R = 2,6-(Me₂NCH₂)₂C₆H₃, E = S, Ar = Ph; <b>2</b>, R = 2,6-(Me₂NCH₂)₂C₆H₃, E = Se, Ar = Ph; <b>3</b>, R = 2,6-(Me₂NCH₂)₂C₆H₃, E = Te, Ar = Ph; <b>6</b>, R = 4-<i>t</i>-Bu-2,6-{P­(O)­(O-<i>i</i>-Pr)₂}₂C₆H₂, E = Se, Ar = Ph; <b>7</b>, R = 4-<i>t</i>-Bu-2,6-{P­(O)­(O-<i>i</i>-Pr)₂}₂C₆H₂, E = Te, Ar = Ph; <b>8</b>, R = 4-<i>t</i>-Bu-2,6-{P­(O)­(O-<i>i</i>-Pr)₂}₂C₆H₂, E = Se, Ar = 2-C₅H₄N) and the corresponding organotin­(IV) compounds RSn­(EAr)₃ (<b>4</b>, R = 2,6-(Me₂NCH₂)₂C₆H₃, E = S, Ar = Ph; <b>5</b>, R = 2,6-(Me₂NCH₂)₂C₆H₃, E = Se, Ar = Ph; <b>10</b>, R = 4-<i>t</i>-Bu-2,6-{P­(O)­(O-<i>i</i>-Pr)₂}₂C₆H₂, E = S, Ar = 2-C₅H₄N), respectively. Compound <b>10</b> undergoes a thermally initiated cyclization reaction to give the benzoxaphosphastannole derivative {1­(P),3­(Sn)-Sn­(S-Py)₂-OP­(O)­(O-<i>i</i>-Pr)-6-<i>t</i>-Bu-4-P­(O)­(O<i>i</i>-Pr)₂}­C₆H₂ (<b>11</b>). The compounds were characterized by ¹H, ¹³C, ³¹P, ¹¹⁹Sn, and ¹²⁵Te NMR and IR spectroscopy, electrospray ionization mass spectrometry, and single-crystal X-ray diffraction analysis. The intramolecular Sn–N and Sn–O distances range between 2.501(3) (<b>2</b>) and 2.815(3) Å (<b>4</b>) and between 2.407(2) (<b>8</b>·C₇H₈) and 2.497(2) Å, respectively. Compounds <b>6</b> and <b>7</b> show intermolecular secondary Sn···Sn interactions at distances of 3.8876(3) and 3.8379(5) Å, respectively