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Synthesis, spectroscopic characterization and structural studies of organotin monothiocarbonates. Crystal structures of Ph3Sn[SCO2Me] and Ph3Sn[SCO2(i-Pr)]
Drake,Yang
, p. 1214 - 1221 (2000)
O-alkyl monothiocarbonate (monoxanthate) derivatives of tin were obtained by the reaction of a sodium salt of the monothiocarbonic acid with an organotin chloride to give Ph3Sn[SCO2R], Ph2Sn[SCO2R]2, and Me3Sn[SCO2R], where R = Me and i-Pr. The compounds have been characterized by infrared, Raman, 1H NMR, and 13C NMR spectroscopy, as well as mass spectrometry, and in two cases by X-ray crystallography. Ph3Sn[SCO2Me] (1) and Ph3Sn[SCO2(i-Pr)] (2), crystallize in the triclinic space group P1 (no. 2) with cell parameters a = 10.218(4), b = 10.568(6), c = 9.366(7) A, α = 106.73(5), β = 96.99(5), γ = 85.55(4)°, V = 960(1) A3, and Z = 2 for 1; and a = 14.793(2), b = 17.856(3), c = 9.813(3) A, α = 103.86(5), β = 98.36(5), γ = 106.85(4)°, V = 2343(1) A3, and Z = 2 for 2. The latter has two molecules in the asymmetric unit. The immediate environment about tin in both 1 and 2 is that of the expected distorted tetrahedron. However, the orientation of the monothiocarbonate group is such that there is an Sn-O intramolecular interaction of 3.040(8) for 1 and 3.05(2) A on average for 2. Thus, the considerable distortion is consistent with a tendency to form a five-coordinate, trigonal bipyramidal species with one of the O-Sn-C angles approaching 180°(153.4(4) for 1 and an average of 157.1(6) for 2). Estimations of the Pauling partial bond orders suggest this weak Sn-O interaction is slightly stronger than the corresponding Ge-O interaction in the analogous germanium derivative, Ph3Ge[SCO2Me].
