Ru and Os complexes containing a P,N-donor heterotopic ligand: The effect of solvent on stereochemistry

Serin L. Dabb; Barbara A. Messerle; Matthew K. Smith; Anthony C. Willis

doi:10.1021/ic7019044

Ru and Os complexes containing a P,N-donor heterotopic ligand: The effect of solvent on stereochemistry

Serin L. Dabb, Barbara A. Messerle, Matthew K. Smith, Anthony C. Willis

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

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Abstract

Ruthenium and osmium complexes of the general formula MCl ₂(PyP)₂ (where PyP is the P,N- donor ligand 1-(2-diphenylphosphinoethyl)pyrazole) were synthesized from MCl ₂(PPh₃)₃ (where M = Ru or Os). Three of the five possible stereoisomers of RuCl₂(PyP)₂ were synthesized and characterized in solution by multinuclear NMR spectroscopy, and the structure of these in the solid state was determined by X-ray crystallography. Two of the analogous Os isomers were also synthesized. It was found that different solvents induced isomerization between these stereoisomers, indicating either lability of the chloride anion or hemilability of the PyP ligand. Bimetallic complexes of the general formula [Ru(μ-Cl)(PyP) ₂]₂[X]₂ were synthesized from chloride abstraction from RuCl₂(PyP)₂ using either silver (X = OSO₂CF₃, BF₄) or sodium (X = BPh₄) salts. The osmium analogue of the Ru bimetallic complexes, [Os(μ-Cl)(PyP) ₂]₂[BPh₄]₂, was also synthesized. Solid-state structures were obtained using X-ray crystallography for the osmium bimetallic complex and the ruthenium bimetallic complex where X = OSO ₂CF₃. The hemilability of PyP was demonstrated through the synthesis of RuCl₂(CO)(κ¹-P-PyP) (κ²-P,N-PyP), which contains one pendant PyP ligand, bound through the P-donor atom.

Original language	English
Pages (from-to)	3034-3044
Number of pages	11
Journal	Inorganic Chemistry
Volume	47
Issue number	8
DOIs	https://doi.org/10.1021/ic7019044
Publication status	Published - 21 Apr 2008
Externally published	Yes

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@article{0d87bb3470bf47eea5a29833913e3ec9,

title = "Ru and Os complexes containing a P,N-donor heterotopic ligand: The effect of solvent on stereochemistry",

abstract = "Ruthenium and osmium complexes of the general formula MCl 2(PyP)2 (where PyP is the P,N- donor ligand 1-(2-diphenylphosphinoethyl)pyrazole) were synthesized from MCl 2(PPh3)3 (where M = Ru or Os). Three of the five possible stereoisomers of RuCl2(PyP)2 were synthesized and characterized in solution by multinuclear NMR spectroscopy, and the structure of these in the solid state was determined by X-ray crystallography. Two of the analogous Os isomers were also synthesized. It was found that different solvents induced isomerization between these stereoisomers, indicating either lability of the chloride anion or hemilability of the PyP ligand. Bimetallic complexes of the general formula [Ru(μ-Cl)(PyP) 2]2[X]2 were synthesized from chloride abstraction from RuCl2(PyP)2 using either silver (X = OSO2CF3, BF4) or sodium (X = BPh4) salts. The osmium analogue of the Ru bimetallic complexes, [Os(μ-Cl)(PyP) 2]2[BPh4]2, was also synthesized. Solid-state structures were obtained using X-ray crystallography for the osmium bimetallic complex and the ruthenium bimetallic complex where X = OSO 2CF3. The hemilability of PyP was demonstrated through the synthesis of RuCl2(CO)(κ1-P-PyP) (κ2-P,N-PyP), which contains one pendant PyP ligand, bound through the P-donor atom.",

author = "Dabb, {Serin L.} and Messerle, {Barbara A.} and Smith, {Matthew K.} and Willis, {Anthony C.}",

year = "2008",

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doi = "10.1021/ic7019044",

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T1 - Ru and Os complexes containing a P,N-donor heterotopic ligand

T2 - The effect of solvent on stereochemistry

AU - Dabb, Serin L.

AU - Messerle, Barbara A.

AU - Smith, Matthew K.

AU - Willis, Anthony C.

PY - 2008/4/21

Y1 - 2008/4/21

N2 - Ruthenium and osmium complexes of the general formula MCl 2(PyP)2 (where PyP is the P,N- donor ligand 1-(2-diphenylphosphinoethyl)pyrazole) were synthesized from MCl 2(PPh3)3 (where M = Ru or Os). Three of the five possible stereoisomers of RuCl2(PyP)2 were synthesized and characterized in solution by multinuclear NMR spectroscopy, and the structure of these in the solid state was determined by X-ray crystallography. Two of the analogous Os isomers were also synthesized. It was found that different solvents induced isomerization between these stereoisomers, indicating either lability of the chloride anion or hemilability of the PyP ligand. Bimetallic complexes of the general formula [Ru(μ-Cl)(PyP) 2]2[X]2 were synthesized from chloride abstraction from RuCl2(PyP)2 using either silver (X = OSO2CF3, BF4) or sodium (X = BPh4) salts. The osmium analogue of the Ru bimetallic complexes, [Os(μ-Cl)(PyP) 2]2[BPh4]2, was also synthesized. Solid-state structures were obtained using X-ray crystallography for the osmium bimetallic complex and the ruthenium bimetallic complex where X = OSO 2CF3. The hemilability of PyP was demonstrated through the synthesis of RuCl2(CO)(κ1-P-PyP) (κ2-P,N-PyP), which contains one pendant PyP ligand, bound through the P-donor atom.

AB - Ruthenium and osmium complexes of the general formula MCl 2(PyP)2 (where PyP is the P,N- donor ligand 1-(2-diphenylphosphinoethyl)pyrazole) were synthesized from MCl 2(PPh3)3 (where M = Ru or Os). Three of the five possible stereoisomers of RuCl2(PyP)2 were synthesized and characterized in solution by multinuclear NMR spectroscopy, and the structure of these in the solid state was determined by X-ray crystallography. Two of the analogous Os isomers were also synthesized. It was found that different solvents induced isomerization between these stereoisomers, indicating either lability of the chloride anion or hemilability of the PyP ligand. Bimetallic complexes of the general formula [Ru(μ-Cl)(PyP) 2]2[X]2 were synthesized from chloride abstraction from RuCl2(PyP)2 using either silver (X = OSO2CF3, BF4) or sodium (X = BPh4) salts. The osmium analogue of the Ru bimetallic complexes, [Os(μ-Cl)(PyP) 2]2[BPh4]2, was also synthesized. Solid-state structures were obtained using X-ray crystallography for the osmium bimetallic complex and the ruthenium bimetallic complex where X = OSO 2CF3. The hemilability of PyP was demonstrated through the synthesis of RuCl2(CO)(κ1-P-PyP) (κ2-P,N-PyP), which contains one pendant PyP ligand, bound through the P-donor atom.

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AN - SCOPUS:43149083280

VL - 47

SP - 3034

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 8

ER -

Ru and Os complexes containing a P,N-donor heterotopic ligand: The effect of solvent on stereochemistry

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