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)]

Jia-Yi Guo; Hong-Wei Xi; Israel Nowik; Rolfe H Herber; Yongxin Li; Kok Hwa Lim; Cheuk-Wai So

doi:10.1021/ic2019633

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)]

Inorg Chem. 2012 Apr 2;51(7):3996-4001. doi: 10.1021/ic2019633. Epub 2012 Mar 12.

Authors

Jia-Yi Guo¹, Hong-Wei Xi, Israel Nowik, Rolfe H Herber, Yongxin Li, Kok Hwa Lim, Cheuk-Wai So

Affiliation

¹ Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, 637371 Singapore.

PMID: 22409480
DOI: 10.1021/ic2019633

Abstract

Reaction of [(PPh(2)═NSiMe(3))(PPh(2)═S)CSn:](2) (1) with elemental sulfur in toluene afforded [{(μ-S)Sn(IV)C(PPh(2)═NSiMe(3))(PPh(2)═S)}(3)Sn(II)(μ(3)-S)] (2) and [CH(2)(PPh(2)═NSiMe(3))(PPh(2)═S)] (3). Compound 2 comprises a Sn(II)S moiety coordinated with the Sn(IV) and S atoms of a trimeric 2-stannathiomethendiide {(PPh(2)═NSiMe(3))(PPh(2)═S)CSn(μ-S)}(3). Compound 2 has been characterized by NMR spectroscopy, (119)Sn Mössbauer studies, X-ray crystallography, and theoretical studies. (119)Sn NMR spectroscopy and Mössbauer studies show the presence of Sn(IV) and Sn(II) atoms in 2. X-ray crystallography suggests that the Sn(II)S 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.