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)Sn^IVC­(PPh₂NSiMe₃)­(PPh₂S)}₃Sn^II(μ₃-S)] (2) and [CH₂(PPh₂NSiMe₃)­(PPh₂S)] (3). Compound 2 comprises a Sn^IIS moiety coordinated with the Sn^IV 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 Sn^IV and Sn^II atoms in 2. X-ray crystallography suggests that the Sn^IIS moiety does not have multiple bond character. Theoretical studies illustrate that the C_methanediide–Sn bonds comprise a lone pair orbital on each C_methanediide atom and an C–Sn occupied σ orbital.