Contrasting Reactivity of 2-Mesityl-1,8-Naphthyridine (Mes-NP) with Singly-Bonded [RhII–RhII] and [RuI–RuI] Compounds

Saha, Barna; Rahaman, S. M. Wahidur; Sinha, Arup; Bera, Jitendra K.

doi:10.1071/ch11060

Cited by 9 publications

(5 citation statements)

References 54 publications

(69 reference statements)

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“…The arrangement of the nonmetalated ligand in these complexes is indicative of side-on axial interaction and not the symmetric ring π-interaction with the metal that was the case for 2-mesityl-1,8-naphthyridine on a Rh II –Rh II core …”

Section: Resultsmentioning

confidence: 91%

“…8 Hz),155.9,155.5,154.5,152.1,142.4,141.5 (d,3 J F−C = 8.4 Hz),140.9,140.4,138.9,137.7,136.6,135.9 (d,3 J F−C = 8.4 Hz), 135.1 (d, 3 J F−C = 8.4 Hz),134.9,127.7,127.3,125.2 (d,2 J F−C = 27.2 Hz), 124.5 (d, 2 J F−C = 25.9 Hz), 124.4, 123.6, 123.1, 119.2 (d, 2 J F−C = 20.4 Hz), 112.5 (d, 2 J F−C = 24 Hz). 19 the SHELX suite of programs, 33 while additional crystallographic calculations were performed by the program PLATON. 34 Figures were drawn using ORTEP32.…”

Section: -(3-methoxyphenylmentioning

confidence: 99%

“…The torsional angles N5− The arrangement of the nonmetalated ligand in these complexes is indicative of side-on axial interaction and not the symmetric ring π-interaction with the metal that was the case for 2-mesityl-1,8-naphthyridine on a Rh II −Rh II core. 19 The metal−metal distances in these complexes deserve comment. It is well recognized that that donor strength of axial ligands regulates the metal−metal distance in a paddlewheel complex.…”

Section: ■ Introductionmentioning

confidence: 99%

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Understanding C–H Bond Activation on a Diruthenium(I) Platform

et al. 2013

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Activation of the C–H bond at the axial site of a [RuI–RuI] platform has been achieved. Room-temperature treatment of 2-(R-phenyl)-1,8-naphthyridine (R = H, F, OMe) with [Ru2(CO)4(CH3CN)6][BF4]2 in CH2Cl2 affords the corresponding diruthenium(I) complexes, which carry two ligands, one of which is orthometalated and the second ligand engages an axial site via a Ru···C–H interaction. Reaction with 2-(2-N-methylpyrrolyl)-1,8-naphthyridine under identical conditions affords another orthometalated/nonmetalated (om/nm) complex. At low temperature (4 °C), however, a nonmetalated complex is isolated that reveals axial Ru···C–H interactions involving both ligands at sites trans to the Ru–Ru bond. A nonmetalated (nm/nm) complex was characterized for 2-pyrrolyl-1,8-naphthyridine at room temperature. Orthometalation of both ligands on a single [Ru–Ru] platform could not be accomplished even at elevated temperature. X-ray metrical parameters clearly distinguish between the orthometalated and nonmetalated ligands. NMR investigation reveals the identity of each proton and sheds light on the nature of [Ru–Ru]···C–H interactions (preagostic/agostic). An electrophilic mechanism is proposed for C–H bond cleavage that involves a C(pπ)–H → σ* [Ru–Ru] interaction, resulting in a Wheland-type intermediate. The heteroatom stabilization is credited to the isolation of nonmetalated complexes for pyrrolyl C–H, whereas lack of such stabilization for phenyl C–H causes rapid proton elimination, giving rise to orthometalation. NPA charge analysis suggests that the first orthometalation makes the [Ru–Ru] core sufficiently electron rich, which does not allow significant interaction with the other axial C–H bond, making the second metalation very difficult.

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Section: Resultsmentioning

confidence: 91%

Section: -(3-methoxyphenylmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Understanding C–H Bond Activation on a Diruthenium(I) Platform

et al. 2013

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“…Shvo [175][176][177] and Gelman's [178][179][180][181][182][183] systems employ -OH unit for alcohol dehydrogenation reactions (Scheme 25d, e). There has been a continuing effort to design bifunctional catalysts on new molecular platforms [51,76,96,101,134,135,[184][185][186][187][188][189][190]. There has been a continuing effort to design bifunctional catalysts on new molecular platforms [51,76,96,101,134,135,[184][185][186][187][188][189][190].…”

Section: Alcohol Dehydrogenation At Axial Site Of a [Ru I -Ru I ] Bondmentioning

confidence: 99%

Homo- and Heterobimetallic Complexes in Catalysis

Kalck¹

2016

Topics in Organometallic Chemistry

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“…Verma's (Indian Institute of Technology-Kanpur) full paper [7] nicely bridges between biomolecules and materials as he describes the synthesis and optical properties of a biotincholesterol conjugate which may be useful in studying biomolecular interactions. Several full papers from Indian authors deal with the structure, preparation and coordination chemistry of several metal complexes: Das [8] (University of Hyberdad) reports three new square planar bis(dithiolene) complexes; Bera and co-workers [9] (Indian Institute of Technology-Kanpur) detail the coordination chemistry of naphthyridine ligands in bimetallic systems; and Chandrasekhar and Bera [10] (Indian Institute of Technology-Kanpur) describe the chemistry of cyclometalated iridium (III) complexes. Finally, Wu [11] (National University of Singapore) provide a review discussing higher order and fused acenes as near-infrared absorbing and emitting compounds of interest to materials chemists.…”

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confidence: 99%