Issue 23, 2013

Tin(ii) fluoridevs.tin(ii) chloride – a comparison of their coordination chemistry with neutral ligands

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

Supplementary files

Article information

Article type
Paper
Submitted
19 Mar 2013
Accepted
12 Apr 2013
First published
15 Apr 2013

Dalton Trans., 2013,42, 8364-8374

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

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements