Methyl Tin(IV) Derivatives of HOTeF₅ and HN(SO₂CF₃)₂:  A Solution Multinuclear NMR Study and the X-ray Crystal Structures of (CH₃)₂SnCl(OTeF₅) and [(CH₃)₃Sn(H₂O)₂][N(SO₂CF₃)₂]

Abstract

The new tin(IV) species (CH(3))(2)SnCl(OTeF(5)) was prepared via either the solvolysis of (CH(3))(3)SnCl in HOTeF(5) or the reaction of (CH(3))(3)SnCl with ClOTeF(5). It was characterized by NMR and vibrational spectroscopy, mass spectrometry, and single crystal X-ray diffraction. (CH(3))(2)SnCl(OTeF(5)) crystallizes in the monoclinic space group P2(1)/n (a = 5.8204(8) A, b =10.782(1) A, c =15.493(2) A, beta = 91.958(2) degrees, V = 971.7(2) A(3), Z = 4). NMR spectroscopy of (CH(3))(3)SnX, prepared from excess Sn(CH(3))(4) and HX (X = OTeF(5) or N(SO(2)CF(3))(2)), revealed a tetracoordinate tin environment using (CH(3))(3)SnX as a neat liquid or in dichloromethane-d(2) (CD(2)Cl(2)) solutions. In acetone-d(6) and acetonitrile-d(3) (CD(3)CN) solutions, the tin atom in (CH(3))(3)SnOTeF(5) was found to extend its coordination number to five by adding one solvent molecule. In the strong donor solvent DMSO, the Sn-OTeF(5) bond is broken and the (CH(3))(3)Sn(O=S(CH(3))(2))(2)(+) cation and the OTeF(5)(-) anion are formed. (CH(3))(3)SnOTeF(5) and (CH(3))(3)SnN(SO(2)CF(3))(2) react differently with water. While the Te-F bonds in the OTeF(5) group of (CH(3))(3)SnOTeF(5) undergo complete hydrolysis that results in the formation of [(CH(3))(3)Sn(H(2)O)(2)](2)SiF(6), (CH(3))(3)SnN(SO(2)CF(3))(2) forms the stable hydrate salt [(CH(3))(3)Sn(H(2)O)(2)][N(SO(2)CF(3))(2)]. This salt crystallizes in the monoclinic space group P2(1)/c (a = 7.3072(1) A, b =13.4649(2) A, c =16.821(2) A, beta = 98.705(1) degrees, V = 1636.00(3) A(3), Z = 4) and was also characterized by NMR and vibrational spectroscopy.

Macromolecular Self‐Assembly of Organotin(IV) Squarates and Croconates – Preparation and Crystal Structures of [SnMe2(H2O)2]C4O4, [SnMe3]2C4O4, and [SnMe3(H2O)]2C5O5

“…While most of these bands can likely be attributed to stretching vibrations of non‐coordinated carbonyl groups,, , the band at approx. 1650 cm –1 probably belongs to a H 2 O deformation vibration . The SnMe 3 fragments in 2 and 3 show characteristic bands at approx.…”

“…Different from compound 1 , the Sn atoms are only five‐coordinate by the three methyl groups and two squarate oxygen atoms, with the oxygen atoms defining the axial positions of a regular trigonal bipyramid (configuration index TBPY‐5‐11). This configuration is the most common observed in R 3 Sn complexes with oxygen ligands rather than an octahedral coordination , . In spite of the lower coordination number of Sn in compound 2 compared to 1 , the Sn–O distances are significantly longer with 227.8(3)–230.4(3) pm.…”

“…The Sn–O bond strength is consequently more strongly influenced by the coordination mode of the ligand than by the coordination number of tin. The Sn–OH 2 separation is with 230.6(2) pm in the same region as in other hydrated organotin(IV) species,, and is slightly larger than in compound 1 . The interatomic distances within the croconate anion are virtually equal with those observed for the squarate anion in 1 and 2 , with the C–O bonds within the tin‐coordinated carbonyl groups slightly elongated.…”

Further Perspectives on the Teflate versus Fluoride Analogy: The Case of a Co(II) Pentafluoroorthotellurate Complex

“…As a side product, Cl 2 is formed, which is removed from the reaction mixture by evaporation. This preparative approach is similar to that used for the synthesis of the related [Ni­(OTeF 5 ) 4 ] 2– and [Au­(OTeF 5 ) 4 ] – homoleptic anions, , therefore entailing yet another example for the practicability of using the hypochlorite ClOTeF 5 , in the synthesis of teflate compounds. ,− …”