Scorpionate Ligands Based on 2-Mercaptopyridine:  A Ligand with a Greater Propensity To Sting?

Gavin Dyson; Alexander Zech; Benjamin W. Rawe; Mairi F. Haddow; Alexander Hamilton; Gareth Owen

doi:10.1021/om200694r

Scorpionate Ligands Based on 2-Mercaptopyridine: A Ligand with a Greater Propensity To Sting?

Gavin Dyson, Alexander Zech, Benjamin W. Rawe, Mairi F. Haddow, Alexander Hamilton, Gareth Owen

Faculty of Computing, Engineering and Science

Research output: Contribution to journal › Article › peer-review

Abstract

The synthesis and characterization of the first platinum group metal complexes of the recently reported ligand [H2B(mp)2]− (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{κ3-SSB-BH(mp)2}(η3-C8H13)] and [Ir(H){κ3-SSB-BH(mp)2}(η4-C8H12)], respectively. Structural characterization of the rhodium complex reveals a notably short rhodium–boron distance of 2.054(2) Å. 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){κ3-SSB-BH(mp)2}(η4-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.

Original language	English
Pages (from-to)	5844-5850
Journal	Organometallics
Volume	30
Issue number	21
DOIs	https://doi.org/10.1021/om200694r
Publication status	Published - 19 Oct 2011

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@article{b2fed9e912cb4637aba5ab765998aa3a,

title = "Scorpionate Ligands Based on 2-Mercaptopyridine: A Ligand with a Greater Propensity To Sting?",

abstract = "The synthesis and characterization of the first platinum group metal complexes of the recently reported ligand [H2B(mp)2]− (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{κ3-SSB-BH(mp)2}(η3-C8H13)] and [Ir(H){κ3-SSB-BH(mp)2}(η4-C8H12)], respectively. Structural characterization of the rhodium complex reveals a notably short rhodium–boron distance of 2.054(2) {\AA}. 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){κ3-SSB-BH(mp)2}(η4-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.",

author = "Gavin Dyson and Alexander Zech and Rawe, {Benjamin W.} and Haddow, {Mairi F.} and Alexander Hamilton and Gareth Owen",

year = "2011",

month = oct,

day = "19",

doi = "10.1021/om200694r",

language = "English",

volume = "30",

pages = "5844--5850",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

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TY - JOUR

T1 - Scorpionate Ligands Based on 2-Mercaptopyridine

T2 - A Ligand with a Greater Propensity To Sting?

AU - Dyson, Gavin

AU - Zech, Alexander

AU - Rawe, Benjamin W.

AU - Haddow, Mairi F.

AU - Hamilton, Alexander

AU - Owen, Gareth

PY - 2011/10/19

Y1 - 2011/10/19

N2 - The synthesis and characterization of the first platinum group metal complexes of the recently reported ligand [H2B(mp)2]− (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{κ3-SSB-BH(mp)2}(η3-C8H13)] and [Ir(H){κ3-SSB-BH(mp)2}(η4-C8H12)], respectively. Structural characterization of the rhodium complex reveals a notably short rhodium–boron distance of 2.054(2) Å. 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){κ3-SSB-BH(mp)2}(η4-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.

AB - The synthesis and characterization of the first platinum group metal complexes of the recently reported ligand [H2B(mp)2]− (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{κ3-SSB-BH(mp)2}(η3-C8H13)] and [Ir(H){κ3-SSB-BH(mp)2}(η4-C8H12)], respectively. Structural characterization of the rhodium complex reveals a notably short rhodium–boron distance of 2.054(2) Å. 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){κ3-SSB-BH(mp)2}(η4-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.

U2 - 10.1021/om200694r

DO - 10.1021/om200694r

M3 - Article

SN - 0276-7333

VL - 30

SP - 5844

EP - 5850

JO - Organometallics

JF - Organometallics

IS - 21

ER -

Scorpionate Ligands Based on 2-Mercaptopyridine: A Ligand with a Greater Propensity To Sting?

Abstract

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