Novel Heteroleptic Stannylenes with Intramolecular O,C,O-Donor Stabilization,

The heteroleptic organotin(II) halides {2,6-[P(O)(OEt)2]2-4-tert-Bu-C6H2}SnX (1, X = Cl; 2, X = Br) have been prepared starting from {2,6-[P(O)(OEt)2]2-4-tert-Bu-C6H2}Li and SnX2 and have been used as precursors for the preparation of the heteroleptic stannylenes {2,6-[P(O)(OEt)2]2-4-tert-Bu-C6H2}SnX (4, X = SPh; 5, X = CH(SiMe3)2; 6, X = SiPh3; 7, X = SnPh3; 7a, X = SnMe3), the tetravalent monorganotin derivatives {{2,6-[P(O)(OEt)2]2-4-tert-Bu-C6H2}SnCl(μ-S)}2 (8) and {2,6-[P(O)(OEt)2]2-4-tert-Bu-C6H2}SnBr3 (9), the diorganotin cation {2,6-[P(O)(OEt)2]2-4-tert-Bu-C6H2}(Ph3C)(Cl)Sn+PF6- (10), and the metal−stannylene complexes {2,6-[P(O)(OEt)2]2-4-tert-Bu-C6H2}(Cl)Sn[M(CO)n] (11, M = W, n = 5; 12, M = Cr, n = 5; 13, M = Fe, n = 4). Multinuclear (1H, 13C, 31P, 119Sn) NMR of all compounds, 119Sn Mössbauer spectra of 1 and 10, and single-crystal X-ray structure analyses of 6, 8, and 12 are reported. The derivatives 6, 7, and 7a are rare examples of compounds containing Sn(II)−Si(IV) and Sn(II)−Sn(IV) bonds, respectively.