Synthesis and Characterisation of Nonclassical Ruthenium Hydride Complexes Containing Chelating Bidentate and Tridentate Phosphine Ligands

Prechtl, Martin H. G.; Ben‐David, Yehoshoa; Giunta, Daniela; Busch, Stefan; Taniguchi, Yuki; Wisniewski, Wolfgang; Görls, Helmar; Mynott, Richard; Theyssen, Nils; Milstein, David; Leitner, Walter

doi:10.1002/chem.200600897

Cited by 69 publications

(58 citation statements)

References 48 publications

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“…Herein we display the defined synthesis and characterisation of complexes 4 and 5 and the modified ruthenium hydride complex 6 bearing an aliphatic PNP ligand with a methylated nitrogen compound, following a typical synthetic protocol of ruthenium dihydrogen complexes. 18 Moreover, we report the reactivity of complex 6 towards B-H bonds. For each complex, we present the first mass spectra of air and moisture sensitive small ruthenium dihydrogen complexes which allowed us a deeper insight into the compositions of our synthesised complexes.…”

Section: Introductionmentioning

confidence: 90%

Synthesis and characterisation of ruthenium dihydrogen complexes and their reactivity towards B–H bonds

et al. 2014

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In this paper the synthesis and characterisation of ruthenium dihydrogen complexes bearing rigid aliphatic PNP pincer-type ligands are described. As one result hydride complexes were synthesised in good to high yields by a one-pot direct hydrogenation reaction. As another finding the dihydrogen complex, stabilised with a N-Me group in the ligand frame, can be converted with dimethylamine borane into a rare σ-boron complex [RuH 2 (BH 3 )(Me-PNP)] with rapid B-N decoupling. Additionally, we present the first mass spectrometric analysis of the synthesised σ-complexes via liquid injection field desorption/ ionisation technique (LIFDI-MS).

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Section: Introductionmentioning

confidence: 90%

Synthesis and characterisation of ruthenium dihydrogen complexes and their reactivity towards B–H bonds

et al. 2014

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“…It is also closely related to the isoelectronic neutral complexes Ru- [61] [dtbpmb = 1,3-bis((di-tert-butylphosphino)methyl)benzyl)] that have been identified as a containing a dihydrogen ligand.…”

Section: Mono-pcyp 3 Complexesmentioning

confidence: 97%

Intramolecular Alkyl Phosphine Dehydrogenation in Cationic Rhodium Complexes of Tris(cyclopentylphosphine)

Douglas

Brayshaw

Dallanegra

et al. 2008

Chemistry A European J

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[Rh(nbd)(PCyp(3))(2)][BAr(F) (4)] (1) [nbd = norbornadiene, Ar(F) = C(6)H(3)(CF(3))(2), PCyp(3) = tris(cyclopentylphosphine)] spontaneously undergoes dehydrogenation of each PCyp(3) ligand in CH(2)Cl(2) solution to form an equilibrium mixture of cis-[Rh{PCyp(2)(eta(2)-C(5)H(7))}(2)][BAr(F) (4)] (2 a) and trans-[Rh{PCyp(2)(eta(2)-C(5)H(7))}(2)][BAr(F) (4)] (2 b), which have hybrid phosphine-alkene ligands. In this reaction nbd acts as a sequential acceptor of hydrogen to eventually give norbornane. Complex 2 b is distorted in the solid-state away from square planar. DFT calculations have been used to rationalise this distortion. Addition of H(2) to 2 a/b hydrogenates the phosphine-alkene ligand and forms the bisdihydrogen/dihydride complex [Rh(PCyp(3))(2)(H)(2)(eta(2)-H(2))(2)][BAr(F) (4)] (5) which has been identified spectroscopically. Addition of the hydrogen acceptor tert-butylethene (tbe) to 5 eventually regenerates 2 a/b, passing through an intermediate which has undergone dehydrogenation of only one PCyp(3) ligand, which can be trapped by addition of MeCN to form trans-[Rh{PCyp(2)(eta(2)-C(5)H(7))}(PCyp(3))(NCMe)][BAr(F) (4)] (6). Dehydrogenation of a PCyp(3) ligand also occurs on addition of Na[BAr(F) (4)] to [RhCl(nbd)(PCyp(3))] in presence of arene (benzene, fluorobenzene) to give [Rh(eta(6)-C(6)H(5)X){PCyp(2)(eta(2)-C(5)H(7))}][BAr(F) (4)] (7: X = F, 8: X = H). The related complex [Rh(nbd){PCyp(2)(eta(2)-C(5)H(7))}][BAr(F) (4)] 9 is also reported. Rapid ( approximately 5 minutes) acceptorless dehydrogenation occurs on treatment of [RhCl(dppe)(PCyp(3))] with Na[BAr(F) (4)] to give [Rh(dppe){PCyp(2)(eta(2)-C(5)H(7))}][BAr(F) (4)] (10), which reacts with H(2) to afford the dihydride/dihydrogen complex [Rh(dppe)(PCyp(3))(H)(2)(eta(2)-H(2))][BAr(F) (4)] (11). Competition experiments using the new mixed alkyl phosphine ligand PCy(2)(Cyp) show that [RhCl(nbd){PCy(2)(Cyp)}] undergoes dehydrogenation exclusively at the cyclopentyl group to give [Rh(eta(6)-C(6)H(5)X){PCy(2)(eta(2)-C(5)H(7))}][BAr(F) (4)] (17: X = F, 18: X = H). The underlying reasons behind this preference have been probed using DFT calculations. All the complexes have been characterised by multinuclear NMR spectroscopy, and for 2 a/b, 4, 6, 7, 8, 9 and 17 also by single crystal X-ray diffraction.

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“…[65] The results from DFT calculations suggested s-bond metathesis as a key step in the exchange mechanism, with a large directing effect from the steric hindrance inferred by the ligand sidearm groups.…”

Section: Homogeneous Catalysismentioning

confidence: 98%

Neutral Tridentate PNP Ligands and Their Hybrid Analogues: Versatile Non‐Innocent Scaffolds for Homogeneous Catalysis

Vlugt¹,

Reek²

2009

Angew Chem Int Ed

420

145

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Ligands in coordination chemistry and homogeneous catalysis are traditionally "static" spectators that do not actively participate in the catalytic cycle. However, such classic systems do not provide additional "handles" that could facilitate or trigger alternative productive reaction pathways. Recent advances in the use of novel nitrogen-centered pincer systems have unveiled interesting opportunities for cooperative catalysis. The chemistry of pyridine-derived, neutral ligands is discussed, with a specific focus on their non-innocent behavior and potential as facilitators for metal-mediated organic transformations. This overview should provide inspiration and an incentive to incorporate non-innocent ligands and their metal complexes within old and new homogeneously catalyzed reactions.

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Synthesis and Characterisation of Nonclassical Ruthenium Hydride Complexes Containing Chelating Bidentate and Tridentate Phosphine Ligands

Cited by 69 publications

References 48 publications

Synthesis and characterisation of ruthenium dihydrogen complexes and their reactivity towards B–H bonds

Synthesis and characterisation of ruthenium dihydrogen complexes and their reactivity towards B–H bonds

Intramolecular Alkyl Phosphine Dehydrogenation in Cationic Rhodium Complexes of Tris(cyclopentylphosphine)

Neutral Tridentate PNP Ligands and Their Hybrid Analogues: Versatile Non‐Innocent Scaffolds for Homogeneous Catalysis

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