Reactivity of a Tin(II) (Iminophosphinoyl)(thiophosphinoyl)methanediide Complex Toward Sulfur: Synthesis and 119Sn Mössbauer Spectroscopic Studies of [{(μ-S)SnC(PPh2NSiMe3)(PPh2S)}3Sn(μ3-S)]

Reaction of [(PPh2NSiMe3)­(PPh2S)­CSn:]2 (1) with elemental sulfur in toluene afforded [{(μ-S)SnIVC­(PPh2NSiMe3)­(PPh2S)}3SnII3-S)] (2) and [CH2(PPh2NSiMe3)­(PPh2S)] (3). Compound 2 comprises a SnIIS moiety coordinated with the SnIV and S atoms of a trimeric 2-stannathiomethendiide {(PPh2NSiMe3)­(PPh2S)­CSn­(μ-S)}3. Compound 2 has been characterized by NMR spectroscopy, 119Sn Mössbauer studies, X-ray crystallography, and theoretical studies. 119Sn NMR spectroscopy and Mössbauer studies show the presence of SnIV and SnII atoms in 2. X-ray crystallography suggests that the SnIIS moiety does not have multiple bond character. Theoretical studies illustrate that the Cmethanediide–Sn bonds comprise a lone pair orbital on each Cmethanediide atom and an C–Sn occupied σ orbital.