Scorpionate Ligands Based on 2-Mercaptopyridine: A Ligand with a Greater Propensity To Sting?
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- 作者：Gavin Dyson ; Alexander Zech ; Benjamin W. Rawe ; Mairi F. Haddow ; Alexander Hamilton ; Gareth R. Owen
- 刊名：Organometallics
- 出版年：2011
- 出版时间：November 14, 2011
- 年：2011
- 卷：30
- 期：21
- 页码：5844-5850
- 全文大小：394K
- 年卷期：v.30,no.21(November 14, 2011)
- ISSN：1520-6041
文摘
The synthesis and characterization of the first platinum group metal complexes of the recently reported ligand [H2B(mp)2]鈭?/sup> (where mp = 2-mercaptopyridyl) are presented herein. Addition of 2 equiv of Na[H2B(mp)2] to [MCl(COD)]2 (where M = Rh, Ir; COD = 1,5-cyclooctadiene) leads to the hydride migration products [Rh{魏3-SSB-BH(mp)2}(畏3-C8H13)] and [Ir(H){魏3-SSB-BH(mp)2}(畏4-C8H12)], respectively. Structural characterization of the rhodium complex reveals a notably short rhodium鈥揵oron distance of 2.054(2) 脜. The reactivity observed for the rhodium complex is different from that of all known scorpionate ligands, suggesting a higher propensity for hydride migration within the 2-mercaptopyridine-based ligands. The complex [Ir(Cl){魏3-SSB-BH(mp)2}(畏4-C8H12)], which is formed via hydride/halide exchange in chloroform, is also structurally characterized. The new complexes provide rare examples of metallaboratrane complexes where one hydrogen substituent remains at the boron center.