The Transition Metal Coordination Chemistry of Hemilabile Ligands

Slone, Caroline S.; Weinberger, Dana A.; Mirkin, Chad A.

doi:10.1002/9780470166499.ch3

Cited by 438 publications

(268 citation statements)

References 514 publications

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“…Treatment of Mn(CO) 5 Br with H 3 B·dppm using Na[BAr [18] only resulted in mixtures of intractable products. Complex 1 has been fully characterised by NMR spectroscopy and X-ray crystallography, which all show that the chelating phosphane-borane adopts a bidentate (η 2 ) bridging mode of the BH 3 group.…”

Section: Resultsmentioning

confidence: 97%

“…solvent) [1] or anion. [2] An alternative mechanism -when a suitable ligand set is available -is one that involves a hemilabile ligand, [3][4][5] in which one donor atom in a chelate ligand has the ability to reversibly decoordinate in a catalytic cycle to reveal a coordinatively unsaturated metal centre. The design of hemilabile ligands is often based on ligands in which one end is a phosphane (which binds strongly) and the other a more weakly ligating group that can move away to generate a vacant site (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

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Chelating Phosphane–Boranes as Hemilabile Ligands – Synthesis of[Mn(CO)₃(η²‐H₃B·dppm)][BAr^F₄] and [Mn(CO)₄(η¹‐H₃B·dppm)][BAr^F₄]

et al. 2006

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Manganese complexes bearing the chelating phosphane–borane ligand H3B·dppm [dppm = bis(diphenylphosphanyl)methane] have been prepared. Addition of H3B·dppm to Mn(CO)5Br using Na[BArF4] as a halide‐abstracting reagent affords [Mn(CO)3(η2‐H3B·dppm)][BArF4] (1). This reacts with CO to open the bidentate borane to afford [Mn(CO)4(η1‐H3B·dppm)][BArF4] (2) in which the borane is now bound in a monodentate manner. The CO addition is reversible, and placing 2 under vacuum (hours) regenerates 1 quantitatively, demonstrating that the chelating phosphane–boranes can act as hemilabile ligands. The complexes 1 and 2 have been fully characterised by NMR spectroscopy and X‐ray crystallography. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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Section: Resultsmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

Chelating Phosphane–Boranes as Hemilabile Ligands – Synthesis of[Mn(CO)₃(η²‐H₃B·dppm)][BAr^F₄] and [Mn(CO)₄(η¹‐H₃B·dppm)][BAr^F₄]

et al. 2006

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“…The 31 P{ 1 H} NMR spectrum of the crude neutral dichloro complex 3 in CDCl 3 showed only one singlet at δ 50.7 ppm. Brown-yellow crystals suitable for single-crystal X-ray diffraction analysis were obtained from acetonitrile in 70 % yield.…”

Section: Resultsmentioning

confidence: 98%

Metal Effects on the Asymmetric Synthesis of a New Heterobidentate As/P=S Ligand

Pullarkat

et al. 2010

Eur J Inorg Chem

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“…252, 253 Typical ligands used for catalysis that make use of their hemilability involve a phosphine and an oxygen donor, such as an ether.…”

Section: Nonrigidity In Hemilabile Ligandsmentioning

confidence: 99%

Stereochemical Nonrigidity of Organometallic Complexes

Faller¹

2005

Encyclopedia of Inorganic Chemistry

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Compounds that undergo intramolecular rearrangements at rates that affect the NMR line shapes in generally accessible temperature ranges are described as stereochemically nonrigid. Analysis of 1D and 2D NMR spectra as a function of temperature often allow the rates, as well as the mechanisms of interconversion of conformers or isomers, to be determined. Examples were selected to illustrate the importance of stereochemical nonrigidity in reactivity and the potential for affecting stereochemistry in the products of reactions.

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The Transition Metal Coordination Chemistry of Hemilabile Ligands

Cited by 438 publications

References 514 publications

Chelating Phosphane–Boranes as Hemilabile Ligands – Synthesis of[Mn(CO)₃(η²‐H₃B·dppm)][BAr^F₄] and [Mn(CO)₄(η¹‐H₃B·dppm)][BAr^F₄]

Chelating Phosphane–Boranes as Hemilabile Ligands – Synthesis of[Mn(CO)₃(η²‐H₃B·dppm)][BAr^F₄] and [Mn(CO)₄(η¹‐H₃B·dppm)][BAr^F₄]

Metal Effects on the Asymmetric Synthesis of a New Heterobidentate As/P=S Ligand

Stereochemical Nonrigidity of Organometallic Complexes

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The Transition Metal Coordination Chemistry of Hemilabile Ligands

Cited by 438 publications

References 514 publications

Chelating Phosphane–Boranes as Hemilabile Ligands – Synthesis of[Mn(CO)3(η2‐H3B·dppm)][BArF4] and [Mn(CO)4(η1‐H3B·dppm)][BArF4]

Chelating Phosphane–Boranes as Hemilabile Ligands – Synthesis of[Mn(CO)3(η2‐H3B·dppm)][BArF4] and [Mn(CO)4(η1‐H3B·dppm)][BArF4]

Metal Effects on the Asymmetric Synthesis of a New Heterobidentate As/P=S Ligand

Stereochemical Nonrigidity of Organometallic Complexes

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Chelating Phosphane–Boranes as Hemilabile Ligands – Synthesis of[Mn(CO)₃(η²‐H₃B·dppm)][BAr^F₄] and [Mn(CO)₄(η¹‐H₃B·dppm)][BAr^F₄]

Chelating Phosphane–Boranes as Hemilabile Ligands – Synthesis of[Mn(CO)₃(η²‐H₃B·dppm)][BAr^F₄] and [Mn(CO)₄(η¹‐H₃B·dppm)][BAr^F₄]