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Scorpionate Ligands Basedon 2-Mercaptopyridine: ALigand with a Greater Propensity To Sting?

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Title: Scorpionate Ligands Basedon 2-Mercaptopyridine: ALigand with a Greater Propensity To Sting?
Authors: Gavin Dyson1, Alexander Zech1, Benjamin W. Rawe1, MairiF. Haddow1, Alexander Hamilton1, Gareth R. Owen1
Source: Organometallics. Nov2011, Vol. 30 Issue 21, p5844-5850. 7p.
Subjects: Complex compounds synthesis, Scorpionates, Ligands (Chemistry), Metal complexes, Platinum group, Rhodium, Reactivity (Chemistry)
Abstract: The synthesis and characterization of the first platinumgroupmetal complexes of the recently reported ligand [H2B(mp)2]−(where mp = 2-mercaptopyridyl) are presentedherein. 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{κ3-SSB-BH(mp)2}(η3-C8H13)] and [Ir(H){κ3-SSB-BH(mp)2}(η4-C8H12)], respectively. Structural characterization of the rhodium complexreveals a notably short rhodium–boron distance of 2.054(2)Å. The reactivity observed for the rhodium complex is differentfrom that of all known scorpionate ligands, suggesting a higher propensityfor hydride migration within the 2-mercaptopyridine-based ligands.The complex [Ir(Cl){κ3-SSB-BH(mp)2}(η4-C8H12)], whichis formed via hydride/halide exchange in chloroform, is also structurallycharacterized. The new complexes provide rare examples of metallaboratranecomplexes where one hydrogen substituent remains at the boron center. [ABSTRACT FROM AUTHOR]
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Abstract:The synthesis and characterization of the first platinumgroupmetal complexes of the recently reported ligand [H2B(mp)2]−(where mp = 2-mercaptopyridyl) are presentedherein. 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{κ3-SSB-BH(mp)2}(η3-C8H13)] and [Ir(H){κ3-SSB-BH(mp)2}(η4-C8H12)], respectively. Structural characterization of the rhodium complexreveals a notably short rhodium–boron distance of 2.054(2)Å. The reactivity observed for the rhodium complex is differentfrom that of all known scorpionate ligands, suggesting a higher propensityfor hydride migration within the 2-mercaptopyridine-based ligands.The complex [Ir(Cl){κ3-SSB-BH(mp)2}(η4-C8H12)], whichis formed via hydride/halide exchange in chloroform, is also structurallycharacterized. The new complexes provide rare examples of metallaboratranecomplexes where one hydrogen substituent remains at the boron center. [ABSTRACT FROM AUTHOR]
ISSN:02767333
DOI:10.1021/om200694r