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Issue 23, 2013
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Tin(II) fluoride vs. tin(II) chloride – a comparison of their coordination chemistry with neutral ligands

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Abstract

Reaction of SnF2 in MeOH with the appropriate neutral N- or O-donor ligands produces [SnF(2,2′-bipy)]2SnF6, [SnF(1,10-phen)]2SnF4 and [SnF2(L)] L = Me3PO, dmso or pyNO). The X-ray structures of [SnF(2,2′-bipy)]2SnF6, [SnF(1,10-phen)]2SnF4 and [SnF2(dmso)], reveal trigonal pyramidal Sn(II) cores with longer fluorine bridges completing distorted 5- or 6-coordination. Attempts to prepare SnF2 adducts with various phosphine or diphosphine ligands in MeCN failed, whilst in CH2Cl2 solution complex reactions involving the solvent occurred. The NHC, 1,3-(2,6-di-isopropylphenyl)imidazol-2-ylidene (IDiPP) and SnF2 produced the imidazolium salt, [IDiPPH]SnF3, the crystal structure of which revealed the first example of a discrete trifluorostannate(II) ion. In contrast, diphosphine complexes of tin(II) chloride formed readily, including [SnCl2{Me2P(CH2)2PMe2}], [SnCl2{o-C6H4(PMe2)2}], [SnCl2{o-C6H4(PPh2)2}] and [(SnCl2)2(μ-Ph2P(CH2)2PPh2)], which were characterised by X-ray crystallography. The structures of [SnCl2{Me2P(CH2)2PMe2}] and [SnCl2{o-C6H4(PMe2)2}] reveal chloride-bridged dimers, but [SnCl2{o-C6H4(PPh2)2}], although also dimeric, has very asymmetric diphosphine coordination best described as κ1. The structures of [(SnCl2)2(μ-Ph2P(CH2)2PPh2)] and of [SnCl{o-C6H4(AsMe2)2}]SnCl3 reveal trigonal pyramidal cores, but with longer Sn⋯Cl bridges affording polymeric structures. The synthesis of [SnCl2(R3EO)2] (R = Ph, E = P or As; and R = Me, E = P) are also reported, along with the structure of [SnCl2(Me3PO)2], which contains distorted tetragonal pyramidal Sn(II) coordination. X-ray structures are also reported for [(PMe3)2CH2][SnCl3]2 and [Ph2P(H)(CH2)2P(H)Ph2][SnCl3]2, obtained as by-products from the attempts to synthesise phosphine complexes, as well as [(o-C6H4(PMe2)2CH2]I2. All complexes were characterised by microanalysis, IR and multinuclear NMR spectroscopy (1H, 19F{1H}, 31P{1H } and, where solubility allowed, 119Sn). Comparisons are drawn with corresponding Sn(IV) and Ge(II) complexes.

Graphical abstract: Tin(ii) fluoride vs. tin(ii) chloride – a comparison of their coordination chemistry with neutral ligands

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Publication details

The article was received on 19 Mar 2013, accepted on 12 Apr 2013 and first published on 15 Apr 2013


Article type: Paper
DOI: 10.1039/C3DT50743B
Dalton Trans., 2013,42, 8364-8374

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    Tin(II) fluoride vs. tin(II) chloride – a comparison of their coordination chemistry with neutral ligands

    C. Gurnani, A. L. Hector, E. Jager, W. Levason, D. Pugh and G. Reid, Dalton Trans., 2013, 42, 8364
    DOI: 10.1039/C3DT50743B

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