Neutral and cationic phosphine and arsine complexes of tin(iv) halides: synthesis, properties, structures and anion influence.

Victoria K Greenacre,Gillian Reid,William Levason,Rhys P King

doi:10.1039/c9dt03683k

Victoria K Greenacre, Gillian Reid + Show 2 more

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https://doi.org/10.1039/c9dt03683k

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Abstract

The reaction of trans-[SnCl4(PR3)2] (R = Me or Et) with trimethylsilyltriflate (TMSOTf) in CH2Cl2 solution substitutes one chloride to form [SnCl3(PR3)2(OTf)]; addition of excess TMSOTf does not substitute further chlorides. The complexes have been fully characterised by microanalysis, IR and multinuclear NMR (1H, 13C{1H}, 19F{1H}, 31P{1H}, 119Sn) spectroscopy. The crystal structure of [SnCl3(PMe3)2(OTf)] revealed mer-chlorines and trans-phosphines. In contrast, trans-[SnBr4(PR3)2], [SnCl4{Et2P(CH2)2PEt2}], [SnCl4{o-C6H4(PMe2)2}] and [SnCl4{o-C6H4(AsMe2)2}] did not react with TMSOTf in CH2Cl2 solution even after 3 days. The arsine complexes, [SnX4(AsEt3)2] (X = Cl, Br), were confirmed as trans-isomers by similar spectroscopic and structural studies, while attempts to isolate [SnI4(AsEt3)2] were unsuccessful and reaction of SnX4 with SbR3 (R = Et, iPr) resulted in reduction to SnX2 and formation of R3SbX2. trans-[SnCl4(AsEt3)2] is converted by TMSOTf into [SnCl3(AsEt3)2(OTf)], whose X-ray structure reveals the same geometry found in the phosphine analogues, with the triflate coordinated. The salts, [SnCl3(PEt3)2][AlCl4] and [SnCl2(PEt3)2][AlCl4]2 were made by treatment of [SnCl4(PEt3)2] with one and two mol. equivalents, respectively, of AlCl3 in anhydrous CH2Cl2, whereas reaction of [SnCl4(AsEt3)2] with AlCl3 produced a mixture including Et3AsCl2 and [Et3AsCl][Sn(AsEt3)Cl5] (the latter identified crystallographically). In contrast, using Na[BArF] (BArF = [B{3,5-(CF3)2C6H3}4]-) produced [SnCl3(PEt3)2][BArF] and also allowed clean isolation of the arsine analogue, [SnCl3(AsEt3)2][BArF]. [SnCl4{o-C6H4(PMe2)2}] also reacts with AlCl3 in CH2Cl2 to form [SnCl3{o-C6H4(PMe2)2}][AlCl4] and [SnCl2{o-C6H4(PMe2)2}][AlCl4]2. Multinuclear NMR spectroscopy on the [AlCl4]- salts show that δ31P and δ119Sn move progressively to high frequency on conversion from the neutral complex to the mono- and the di-cations, whilst 1J(119Sn-31P) follow the trend: [SnCl3{o-C6H4(PMe2)2}]+ > [SnCl4{o-C6H4(PMe2)2}] > [SnCl2{o-C6H4(PMe2)2}]2+. DFT studies on selected complexes show only small changes in ligand geometries and bond lengths between the halide and triflate complexes, consistent with the X-ray crystallographic data reported and the HOMO and LUMO energies are relatively unperturbed upon the introduction of (coordinated) triflate, whereas the energies of both are ca. 4 eV lower in the cationic species and reveal significant hybridisation across the pnictine ligands.

Highlights

Much of the coordination chemistry of the transition metal ions with neutral ligands is based around metal halide complexes.[1]
Complexes of the tin(IV) halides, SnX4 (X = Cl or Br), with neutral phosphine and arsine ligands have been explored in considerable detail[5] and almost all are of the octahedral trans[SnX4(ER3)2] or cis-[SnX4(bidentate)] types
The neutral tin(IV) phosphine complexes used in this study were made by literature methods or minor modifications thereof, viz[SnCl4(PEt3)2],17 [SnCl4(PMe3)2],16 [SnBr4(PMe3)2],16 [SnCl4{oC6H4(PMe2)2}],4 [SnCl4(Et2PCH2CH2PEt2)],4 as was [SnCl4{oC6H4(AsMe2)2}]

Summary

Introduction

Much of the coordination chemistry of the transition metal ions with neutral ligands is based around metal halide complexes.[1]. [SnCl4(PEt3)2] (0.200 g, 0.40 mmol) was suspended in CH2Cl2 (5 ml), to this AlCl3 (0.107 g, 0.80 mmol) was added, the suspension was stirred for 2 h leaving a clear and colourless solution; the solution was concentrated to dryness and washed with Et2O (3 × 10 ml) dried in vacuo leaving a sticky white solid.

Results

Conclusion