Pyridine Ring Opening at Room Temperature at a Rhenium Tricarbonyl Bipyridine Complex

Huertos, Miguel A.; Pérez, Julio; Riera, Lucı́a

doi:10.1021/ja801655d

Cited by 65 publications

(62 citation statements)

References 25 publications

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“…The most informative features of the 1 H NMR spectrum of 3 are the signals between 4.36 and 6.00 ppm, corresponding to the hydrogen atoms of a dearomatized 2‐pyridyl ring. Similar shielded signals were found in the 1 H NMR spectra of previously characterized products of nucleophilic attack at one pyridyl ring 1. 12 In addition, the 1 H NMR spectrum of 3 includes two different P‐bonded methyl groups and two disastereotopic hydrogens on a P‐bonded methylene group.…”

Section: Methodssupporting

confidence: 67%

“…Interligand CC coupling initiated by deprotonation of appropriately positioned CH groups has been demonstrated in a few examples. Thus, N ‐alkylimidazoles have been coupled with bipy or phen (1,10‐phenanthroline),1 other N ‐alkylimidazoles,2 nitriles, isonitriles,3 CO,4 and monodentate pyridines 5. Similar couplings of monodentate pyridines, followed by oxidation, afforded bipyridines 5b.…”

Section: Methodsmentioning

confidence: 99%

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Deprotonation of Coordinated Phosphanes in a Rhenium Complex: CC Coupling with Diimine Coligands

Arévalo

Pérez

Riera

2015

Chemistry A European J

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The reaction of fac‐[Re(bipy)(CO)3(PMe3)][OTf] (bipy=2,2′‐bipyridine) with KN(SiMe3)2 affords two neutral products: cis,trans‐[Re(bipy)(CO)2(CN)(PMe3)], and a thermally unstable compound, which features a new CC bond between a P‐bonded methylene group (from methyl group deprotonation) and the C6 position of bipy. The solid‐state structures of more stable 1,2‐bis[(2,6‐diisopropylphenyl)imino]acenaphthene analogs, resulting from the deprotonation of PMe3, PPhMe2, and PPh2Me ligands, are determined by X‐ray diffraction.

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Section: Methodssupporting

confidence: 67%

Section: Methodsmentioning

confidence: 99%

Deprotonation of Coordinated Phosphanes in a Rhenium Complex: CC Coupling with Diimine Coligands

Arévalo

Pérez

Riera

2015

Chemistry A European J

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“…[8] About at the same time, we found that the deprotonation reaction of the analogous rhenium compounds, [ReA C H T U N G T R E N N U N G (bipy)(CO) 3 A C H T U N G T R E N N U N G (N-RIm)]OTf (R = methyl, mesityl; OTf = triflate), led to a completely different kind of product. [9] As shown in Scheme 1b, the re-A C H T U N G T R E N N U N G action of the rhenium species with a strong base deprotonated the imidazole C2 À H group, and the so formed carbeniate attacked a C ortho of the adjacent 2,2'-bipyridine ligand. As a consequence, C À C coupling and loss of aromaticity of the involved ring were observed.…”

Section: -C 4 H 7 )A C H T U N G T R E N N U N G (Bipy)(co) 2 a C H Tmentioning

confidence: 99%

Imidazole to NHC Rearrangements at Molybdenum Centers: An Experimental and Theoretical Study

Brill

Dı́az

Huertos

et al. 2011

Chemistry A European J

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Both manganese and rhenium complexes of the type [M(bipy)(CO)(3)(N-RIm)](+) (bipy=2,2'-bipyridine) undergo deprotonation of the central CH group of the N-alkylimidazole (N-RIm) ligand when treated with a strong base. However, the outcome of the reaction is very different for either metal. For Mn, the addition of the equimolar amount of an acid to the product of the deprotonation affords an N-heterocyclic carbene (NHC) complex, whereas for Re, once the deprotonation of the central imidazole CH group has occurred, the bipy ligand undergoes a nucleophilic attack on an ortho carbon, affording the C-C coupling product. The extension of these studies to pseudo-octahedral [Mo(η(3)-allyl)(bipy)(CO)(2)(N-RIm)](+) complexes has allowed us to isolate cationic NHC complexes (Mn(I)-type behavior), as well as their neutral imidazol-2-yl precursors. Theoretical studies of the reaction mechanisms using DFT computations were carried out on the deprotonation of [Mn(bipy)(CO)(3)(N-PhIm)](+), [Re(bipy)(CO)(3) (N-MesIm)](+), and [Mo(η(3)-C(4)H(7))(bipy)(CO)(2) (N-MesIm)](+) complexes (Mes=mesityl) at the B3LYP/6-31G(d) (LANL2DZ for Mn, Re, and Mo) level of theory. Our results explain why different products have been found experimentally for Mn, Mo, and Re complexes. For Re, the process leading to a C-C coupling product is clearly more favored than those forming an imidazol-2-yl product. In contrast, for Mn and Mo complexes, the lower stabilizing interaction between the central imidazole and ortho bipy C atoms, along with the higher lability of the ligands, make the formation of an NHC-type product kinetically more accessible, in good agreement with experimental findings.

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“…In the case of titanium, a titanium alkylidyne is a proposed intermediate. Recently, a few examples of aromatic N-heterocycle cleavage by late transition metal complexes have also been reported; these systems involve rhenium [15,16] and tungsten metal centers [17].…”

Section: Introductionmentioning

confidence: 99%

Ring opening of aromatic heterocycles by uranium complexes

Duhović

Monreal

Diaconescu

2010

Journal of Organometallic Chemistry

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Pyridine Ring Opening at Room Temperature at a Rhenium Tricarbonyl Bipyridine Complex

Cited by 65 publications

References 25 publications

Deprotonation of Coordinated Phosphanes in a Rhenium Complex: CC Coupling with Diimine Coligands

Deprotonation of Coordinated Phosphanes in a Rhenium Complex: CC Coupling with Diimine Coligands

Imidazole to NHC Rearrangements at Molybdenum Centers: An Experimental and Theoretical Study

Ring opening of aromatic heterocycles by uranium complexes

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