Flexible scorpionates for transfer hydrogenation: the first example of their catalytic application

Tsoureas, Nikolaos; Owen, Gareth R.; Hamilton, Alexander; Orpen, A. Guy

doi:10.1039/b809247h

Cited by 41 publications

(44 citation statements)

References 49 publications

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“…Such complexes could have wide ranging application in catalytic processes, indeed any reactivity that requires the generation an empty coordination site. We have recently carried out some preliminary studies exploring such potential [60] and are investigating strategies for the simple removal of boron-labilised ligands.…”

Section: Discussionmentioning

confidence: 99%

Crystal field arguments to explain the trans labilisation within transition metal–borane complexes

Owen

2009

Transition Met Chem

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There has been great interest in metal-borane complexes following the discovery of metallaboratrane complexes in 1999. These complexes contain unusual Z-type (r-acceptor) coordination of borane functional groups and have been shown to provide unexpected coordination geometries and properties for a transition metal in a particular oxidation state. Additionally, such ligands exhibit unusually high trans influences only in certain geometries. Herein, a simple qualitative description, based on crystal field theory arguments, is presented for the explanation of the geometries and atypical trans labilisations observed.

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Section: Discussionmentioning

confidence: 99%

Crystal field arguments to explain the trans labilisation within transition metal–borane complexes

Owen

2009

Transition Met Chem

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“…The B-H-metal interaction therefore has a particular stabilising effect in the flexible scorpionates since it leads to the formation of two six-membered rings rather than one eight-membered ring. 16 As a result of this, both k 3 -SSS and k 3 -SSH coordination modes are commonly observed within complexes containing the Tm ligand. (6)] in solution.…”

Section: Synthesis and Characterisation Of Copper Complexesmentioning

confidence: 97%

A new family of flexible scorpionate ligands based on 2-mercaptopyridine

et al. 2009

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A new family of flexible scorpionate ligands based on 2-mercaptopyridine is reported. The tris- and bis-substituted ligands, K[HB(mp)(3)] (1) and Na[H(2)B(mp)(2)] (2) (mp = 2-mercaptopyridine) have been prepared and fully characterised. The structural characterisation of 1 reveals an unprecedented mu(3)-kappa(3)-SS'H-eta(1)eta(1)eta(2)-kappa(2)-S''C-eta(1)eta(1)-kappa(1)-S'-eta(1) coordination mode. The coordination of both 1 and 2 to copper(I) complexes containing triphenylphosphine and tricyclohexylphosphine co-ligands is investigated suggesting kappa(3)-SSS coordination modes for [Cu{HB(mp)(3)}(PR(3))] {where R = Ph (3); R = Cy, (4)} and kappa(3)-SSH coordination modes for [Cu{H(2)B(mp)(2)}(PR(3))] {where R = Ph (5); R = Cy (6)} the latter confirmed by structural characterisation of 5. A structural comparison with the sulfur based scorpionates, HB(mt)(3) and H(2)B(mt)(2) (mt = methyl-2-mercaptoimidazole) is made in terms of the degree of tautomerisation of the heterocyclic rings.

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“…4,5 First-row metallaboratranes and related compounds that contain a retrodative M→B σ-interaction 6 are appealing as catalysts 7 because of the boron center’s ability to stabilize low valent metals. 8 Akin to frustrated Lewis pairs, 9 it has also been recently demonstrated that the metal-boron interaction can cooperatively facilitate the activation of H 2 .…”

Section: Introductionmentioning

confidence: 99%

“…8 Akin to frustrated Lewis pairs, 9 it has also been recently demonstrated that the metal-boron interaction can cooperatively facilitate the activation of H 2 . 5,7 For instance, our lab recently reported that the diphosphine-borane nickel ( Mes DPB Ph )Ni complex undergoes reversible oxidative addition of H 2 to afford a nickel-borohydrido-hydride complex (Scheme 1). 10 This nickel system is an efficient catalyst for olefin hydrogenation.…”

Section: Introductionmentioning

confidence: 99%

Heterolytic H₂ Cleavage and Catalytic Hydrogenation by an Iron Metallaboratrane

et al. 2013

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Reversible, heterolytic addition of H2 across an iron-boron bond in a ferraboratrane with formal hydride transfer to the boron gives iron-borohydrido-hydride complexes. These compounds catalyze the hydrogenation of alkenes and alkynes to the respective alkanes. Notably, the boron is capable of acting as a shuttle for hydride transfer to substrates. The results are interesting in the context of heterolytic substrate addition across metal-boron bonds in metallaboratranes and related systems, as well as metal-ligand bifunctional catalysis.

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Flexible scorpionates for transfer hydrogenation: the first example of their catalytic application

Cited by 41 publications

References 49 publications

Crystal field arguments to explain the trans labilisation within transition metal–borane complexes

Crystal field arguments to explain the trans labilisation within transition metal–borane complexes

A new family of flexible scorpionate ligands based on 2-mercaptopyridine

Heterolytic H₂ Cleavage and Catalytic Hydrogenation by an Iron Metallaboratrane

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Flexible scorpionates for transfer hydrogenation: the first example of their catalytic application

Cited by 41 publications

References 49 publications

Crystal field arguments to explain the trans labilisation within transition metal–borane complexes

Crystal field arguments to explain the trans labilisation within transition metal–borane complexes

A new family of flexible scorpionate ligands based on 2-mercaptopyridine

Heterolytic H2 Cleavage and Catalytic Hydrogenation by an Iron Metallaboratrane

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Heterolytic H₂ Cleavage and Catalytic Hydrogenation by an Iron Metallaboratrane