Synthesis and structures of thiamacrocycle stabilised cations and dications of M(II) (M = Ge, Sn, Pb) Rhys King, W. Levason, G. Reid University of Southampton, UK Since then, examples with other hard ligands like crown ethers and azamacrocycles have been reported. 2,3 We recently described an unusual family of Ge(II) dications stabilised by the much softer phosphine and arsine ligands, however, there are no examples with soft thioether coordination. 4 Divalent Group 14 dications have been shown to act as both Lewis acids through coordination to electron pair donors and Lewis bases towards Ag(I) and Au(I). 5,6
We present the first examples of M(II) dications and monocations stabilised by thiamacrocyclic coordination. The effect of changing the ring size, metal and anion will be discussed, with the structures and bonding in the cations being investigated through crystallographic and DFT studies. The implications of this on possible new reactivity will be explored. References 1. P. A. Rupar, V. N. Staroverov, K. M. Baines, Science, 2008, 322 , 1360-1362. 2. R. Bandyopadhyay, B. F. T. Cooper, A. J. Rossini, R. W. Schurko and C. L. B. Macdonald, J. Organomet. Chem. , 2010, 695 , 1012–1018. 3. F. Cheng, A. L. Hector, W. Levason, G. Reid, M. Webster and W. Zhang, Angew. Chem. Int Ed ., 2009, 48 , 5152. 4. R. P. King, V. K. Greenacre, W. Levason, J. M. Dyke and G. Reid, Inorg. Chem. , 2021, 60 , 12100–12108 5. R. Bandyopadhyay, J. H. Nguyen, A. Swidan and C. L. B. Macdonald, Angew. Chemie Int. Ed. , 2013, 52 , 3469–3472. 6. R. K. Raut and M. Majumdar, Chem. Commun. , 2017, 53 , 1467–1469.
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