Reactivity of Organotin(I) Dimers RSnSnR (R=2,6-(Me2NCH2)2C6H3, 4-t-Bu-2,6-{P(O)(O-i-Pr)2}2C6H2) with Diary! 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 diary! dichalcogenides ArEEAr provided, depending on the ratio of the reactants, the intramolecularly coordinated heteroleptic organotin(II) chalcogenoarylates RSnEAr (1, R = 2,6-(Me2NCH2)(2)C6H3, -E = S, Ar = Ph; 2, R = 2,6-(Me2NCH2)(2)C6H3, E = Se, Ar = Ph; 3, R = 2,6(Me2NCH2)(2)C6H3, E Te, Ar = Ph; 6, R = 4-t-Bu-2,6-{P(O)(O-i-ET)z}(2)C6H2, E = Se, Ar = Ph; 7, R = 4-t-Bu-2,6-{P(O)(O-i-Pr)(2)}(2)C6H2, E = Te, Ar = Ph; 8, R = 4-t-Bu-2,6-{P(O)(O-i-Pr)(2)}(2)C6H2, E = Se, Ar = 2-C5H4N) and the corresponding organotin(IV) compounds RSn(EAr)(3) (4, R = 2,6-(Me2NCH2)(2)C6H3, E = S, Ar = Ph; 5, R = 2,6-(Me2NCH2)(2)C6H3, E = Se, Ar = Ph; 10, R = 4-t-Bu-2,6-{P(O)(O-i-PO2}(2)C6H2, E = S, Ar = 2-C5H4N), respectively. Compound 1O undergoes a thermally initiated cyclization reaction to give the benzoxaphosphastannole derivative {1(P),3(Sn)-Sn(S-Py)2-OP(O)(O-i-Pr)-6-t-Bu-4-P(O)(Oi-Pr)2}C6H2 (11). The compounds were characterized by H-1, C-13, P-31,Sn-119, and Te-125 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) (2) and 2.815(3) angstrom (4) and between 2.407(2) (8 center dot C7H8) and 2.497(2) angstrom, respectively. Compounds 6 and 7 show intermolecular secondary Sn center dot center dot center dot Sn interactions at distances of 3.8876(3) and 3.8379(5) A, respectively.