RESUMEN
This mini-review provides a brief overview of the use of NMR diffusion methods in connection with estimating molecular weights in solution, recognizing hydrogen bonding and encapsulation processes and, primarily, identifying and estimating the varying degrees of ion pairing. Copyright © 2016 John Wiley & Sons, Ltd.
RESUMEN
NMR diffusion methods continue to attract increasing attention from practising chemists. This short article summarizes some of the more recent developments and highlights the areas in which these methods are finding application, specifically: estimating molecular volumes; investigating the degree of aggregation (especially in salts); studying host-guest interactions; recognizing hydrogen bonds; and directly proving the presence and extent of ion pairing.
RESUMEN
The Pd-catalyzed intramolecular allylic alkylation of unsaturated amides to give γ- and δ-lactams has been studied in the presence of chiral ligands. Ligand (R)-3,5-tBu-MeOBIPHEP (MeOBIPHEP = 6,6'-dimethoxybiphenyl-2,2-diyl)bis(diphenylphosphine)) afforded the best results and allowed the cyclization reactions to take place in up to 94:6 enantiomeric ratio. A model Pd-allyl complex has been prepared and studied through NMR spectroscopic analysis, which provided insight into the processes responsible for the observed enantiomeric ratios. DFT studies were used to characterize the diastereomeric reaction pathways. The calculated energy differences were in good agreement with the experimentally observed enantiomeric ratios.
RESUMEN
Treatment of Ru(PPh(3))(3)HCl with the pincer phosphines 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (xantphos), bis(2-diphenylphosphinophenyl)ether (DPEphos), or (Ph(2)PCH(2)CH(2))(2)O affords Ru(P-O-P)(PPh(3))HCl (xantphos, 1a; DPEphos, 1b; (Ph(2)PCH(2)CH(2))(2)O, 1c). The X-ray crystal structures of 1a-c show that all three P-O-P ligands coordinate in a tridentate manner through phosphorus and oxygen. Abstraction of the chloride ligand from 1a-c by NaBAr(4)(F) (BAr(4)(F) = B(3,5-C(6)H(3)(CF(3))(2))(4)) gives the cationic aqua complexes [Ru(P-O-P)(PPh(3))(H(2)O)H]BAr(4)(F) (3a-c). Removal of chloride from 1a by AgOTf yields Ru(xantphos)(PPh(3))H(OTf) (2a), which reacts with water to form [Ru(xantphos)(PPh(3))(H(2)O)H](OTf). The aqua complexes 3a-b react with O(2) to generate [Ru(xantphos)(PPh(3))(eta(2)-O(2))H]BAr(4)(F) (5a) and [Ru(DPEphos)(PPh(3))(eta(2)-O(2))H]BAr(4)(F) (5b). Addition of H(2) or N(2) to 3a-c yields the thermally unstable dihydrogen and dinitrogen species [Ru(P-O-P)(PPh(3))(eta(2)-H(2))H]BAr(4)(F) (6a-c) and [Ru(P-O-P)(PPh(3))(N(2))H]BAr(4)(F) (7a-c), which have been characterized by multinuclear NMR spectroscopy at low temperature. Ru(PPh(3))(3)HCl reacts with 1,1'-bis(diphenylphosphino)ferrocene (dppf) to give the 16-electron complex Ru(dppf)(PPh(3))HCl (1d), which upon treatment with NaBAr(4)(F), affords [Ru(dppf){(eta(6)-C(6)H(5))PPh(2)}H]BAr(4)(F) (8), in which the PPh(3) ligand binds eta(6) through one of the PPh(3) phenyl rings. Reaction of 8 with CO or PMe(3) at elevated temperatures yields the 18-electron products [Ru(dppf)(PPh(3))(CO)(2)H]BAr(F)(4) (9) and [Ru(PMe(3))(5)H]BAr(4)(F) (10).
RESUMEN
Reaction of the purple tetrakiscarbene ruthenium cation [Ru(I(i)Pr(2)Me(2))(4)H](+) (1, I(i)Pr(2)Me(2) = 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene) with oxygen affords the pink eta(2)-O(2) hydride species [Ru(I(i)Pr(2)Me(2))(4)(eta(2)-O(2))H](+) (2). 2 displays (i) a very facile, reversible O(2) coordination and (ii) an unexpectedly positive hydride chemical shift, and both these features can be predicted and explained by density functional theory (DFT) calculations.
RESUMEN
Pulsed gradient spin-echo (PGSE) diffusion characteristics for a) the new [brucinium][X] salts 6 a-f [a: X = BF(4)(-); b: X = PF(6)(-); c: X = MeSO(3)(-), d: X = CF(3)SO(3)(-); e: X = BArF(-); f: X = PtCl(3)(C(2)H(4))(-)], b) 4-tert-butyl-N-benzyl analogue, 7 and c) the aryl carbocations (p-R-C(6)H(4))(2)CH 9 a (R = CH(3)O) and 9 b (R = (CH(3))(2)N), (p-CH(3)O-C(6)H(4))(x)CPh(3-x)(+) 10 a-c (x = 1-3, respectively) and (p-R-C(6)H(4))(3)C(+) 11 (R = (CH(3))(2)N) and 12 (R = H) all in several different solvents, are reported. The solvent dependence suggests strong ion pairing in CDCl(3), intermediate ion pairing in CD(2)Cl(2) and little ion pairing in [D(6)]acetone. (1)H, (19)F HOESY NMR spectra (HOESY: heteronuclear Overhauser effect spectroscopy) for 6 and 7 reveal a specific approach of the anion with respect to the brucinium cation plus subtle changes, which are related to the anion itself. Further, for carbocations 9-12, (all as BF(4)(-) salts) based on the NOE results, one finds marked changes in the relative positions of the BF(4)(-) anion. In these aryl cationic species the anion can be located either a) very close to the carbonium ion carbon b) in an intermediate position or c) proximate to the N or O atom of the p-substituent and remote from the formally positive C atom. This represents the first example of such a positional dependence of an anion on the structure of the carbocation. DFT calculations support the experimental HOESY results. The solid-state structures for 6 c and the novel Zeise's salt derivative, [brucinium][PtCl(3)(C(2)H(4))], 6 f, are reported. Analysis of (195)Pt NMR and other NMR measurements suggest that the eta(2)-C(2)H(4) bonding to the platinum centre in 6 f is very similar to that found in K[PtCl(3)(C(2)H(4))]. Field dependent T(1) measurements on [brucinium][PtCl(3)(C(2)H(4))] and K[PtCl(3)(C(2)H(4))], are reported and suggested to be useful in recognizing aggregation effects.
Asunto(s)
Iones/química , Sales (Química)/química , Gráficos por Computador , Cristalografía por Rayos X , Espectroscopía de Resonancia Magnética , Modelos Moleculares , SolventesRESUMEN
Green and fast: Allylation of aromatic and aliphatic thiols, by using allyl alcohols as substrates, requires only minutes at ambient temperature with a Ru catalyst (see scheme). Quantitative conversion is normal and the catalyst possesses high functional-group tolerance.The allylation of aromatic and aliphatic thiols, by using allyl alcohols as substrates, requires only minutes at ambient temperature with either a Ru(IV) catalyst, [Ru(Cp*)(eta(3)-C(3)H(5))(CH(3)CN)(2)](PF(6))(2) (2; Cp*=pentamethylcyclopentadienyl) or a combination of [Ru(Cp*)(CH(3)CN)(3)](PF(6)) and camphor sulfonic acid. Quantitative conversion is normal and the catalyst possesses high functional-group tolerance. The use of [Ru(Cp*)(CH(3)CN)(3)](PF(6)) alone affords poor results. A comparison is made to the results from catalytic runs based on the use of carbonates rather than alcohols, by using 2 as the catalyst, and it is shown that the products from the alcohols are formed faster, so there is no advantage in using a carbonate substrate. The observed branched-to-linear (b/l) ratios when using substituted alcohols decrease with time suggesting that the catalysts isomerise the products. A new methodology from which one can select the desired isomeric product is proposed. DFT calculations and NMR spectroscopic measurements, by using an arene sulfonic acid as co-catalyst, suggest that eta(6)-complexes are not relevant for the catalytic system. Moreover, the DFT results indicate that 1) any eta(6)-complexes from the acids RC(6)H(4)SO(3)H result from deprotonation of the acid, 2) complexation of the thiol, via the deprotonated sulfur atom, is preferred over complexation of the O atom of the sulfonate, RC(6)H(4)SO(3) (-) and 3) a sulfonate O-atom complex will be difficult to detect.
RESUMEN
The five-coordinate ruthenium N-heterocyclic carbene (NHC) hydrido complexes [Ru(IiPr(2)Me(2))(4)H][BAr(F) (4)] (1; IiPr(2)Me(2)=1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene; Ar(F)=3,5-(CF(3))(2)C(6)H(3)), [Ru(IEt(2)Me(2))(4)H][BAr(F) (4)] (2; IEt(2)Me(2)=1,3-diethyl-4,5-dimethylimidazol-2-ylidene) and [Ru(IMe(4))(4)H][BAr(F) (4)] (3; IMe(4)=1,3,4,5-tetramethylimidazol-2-ylidene) have been synthesised following reaction of [Ru(PPh(3))(3)HCl] with 4-8 equivalents of the free carbenes at ambient temperature. Complexes 1-3 have been structurally characterised and show square pyramidal geometries with apical hydride ligands. In both dichloromethane or pyridine solution, 1 and 2 display very low frequency hydride signals at about delta -41. The tetramethyl carbene complex 3 exhibits a similar chemical shift in toluene, but shows a higher frequency signal in acetonitrile arising from the solvent adduct [Ru(IMe(4))(4)(MeCN)H][BAr(F) (4)], 4. The reactivity of 1-3 towards H(2) and N(2) depends on the size of the N-substituent of the NHC ligand. Thus, 1 is unreactive towards both gases, 2 reacts with both H(2) and N(2) only at low temperature and incompletely, while 3 affords [Ru(IMe(4))(4)(eta(2)-H(2))H][BAr(F) (4)] (7) and [Ru(IMe(4))(4)(N(2))H][BAr(F) (4)] (8) in quantitative yield at room temperature. CO shows no selectivity, reacting with 1-3 to give [Ru(NHC)(4)(CO)H][BAr(F) (4)] (9-11). Addition of O(2) to solutions of 2 and 3 leads to rapid oxidation, from which the Ru(III) species [Ru(NHC)(4)(OH)(2)][BAr(F) (4)] and the Ru(IV) oxo chlorido complex [Ru(IEt(2)Me(2))(4)(O)Cl][BAr(F) (4)] were isolated. DFT calculations reproduce the greater ability of 3 to bind small molecules and show relative binding strengths that follow the trend CO >> O(2) > N(2) > H(2).
RESUMEN
New Ru-sulfonate catalysts have been synthesized and shown to very rapidly allylate indole and pyrrole compounds using allyl alcohols as substrates. The observed regioselectivity is exceptionally high (up to 100% of the branched isomer). Density functional theory calculations explain these results.
Asunto(s)
Compuestos Alílicos/química , Indoles/química , Propanoles/química , Pirroles/química , Compuestos Alílicos/síntesis química , Catálisis , Indoles/síntesis química , Modelos Moleculares , Pirroles/síntesis química , Compuestos de Rutenio/síntesis química , Compuestos de Rutenio/química , Ácidos Sulfónicos/síntesis química , Ácidos Sulfónicos/químicaRESUMEN
The atropisomeric chelating auxiliaries MeO-Biphep, Binap, MOP and selected monodentate phosphoramidite type ligands are all capable of using differing aromatic fragments as donors to stabilize coordinatively unsaturated 14- or 16-electron species. MeO-Biphep and Binap make use of a double bond immediately adjacent to one of the P-donors to turn these chelate ligands into six-electron donors. In addition to the P-atom, the MOP class uses the pi-electrons of the naphthyl group, not attached to the phosphorus atom, to form a 4e chelate ligand. The MeO-MOP ligands often form weak sigma-bonds, derived from the electrons in this naphthyl ring, rather than pi-olefin complexes. Phosphoramidites, and some related ligands such as "simple-phos", use a pendant phenyl group to form an eta(2)-arene, P-chelate. The various bonding modes have been investigated via X-ray, NMR and DFT studies.
RESUMEN
The new Ru(IV) salt, [Ru(eta(3)-C(3)H(5))(Cp*)(CH(3)CN)(2)](PF(6))(2), is an excellent catalyst for the regioselective allylation of a variety of indole compounds using allyl alcohol as substrate; there are no co-catalysts required in this chemistry and the yields and reaction conditions are very favorable.
Asunto(s)
Indoles/síntesis química , Compuestos Organometálicos/química , Propanoles/química , Rutenio/química , Alquilación , Catálisis , Indoles/química , Estructura Molecular , EstereoisomerismoRESUMEN
1H and 19F Pulsed Gradient Spin Echo (PGSE) diffusion data, together with 1H, 19F-HOESY results are shown to distinguish between different types of anion/cation interactions in chiral dihydrido-P,N-complexes of Ir(III); in CD2Cl2 the diffusion coefficients, D, for the BArF and the Ir-cation suggest ion-pairing whereas the D-values for PF6-reveal independent motion; the PF6- approaches the cation via a specific pathway; the combined PGSE/HOESY approach offers a unique opportunity for exploring anion effects in organometallic/catalytic chemistry.
RESUMEN
PGSE diffusion, 19F, 1H HOESY and 13C NMR studies for a series of [Ru(Cp*)(eta6-arene)][PF6] (1) salts are presented. The solid-state structure of [Ru(Cp*)(eta6-fluorobenzene)][PF6] (1 c) is reported. The extent of the ion pairing and the relative positions of the ions are shown to depend on the arene. For the solvent dichloromethane, new and literature PGSE data for PF6(-) salts of transition-metal, inorganic, and organic salts are compared. Taken together, these new results show that the charge distribution and the ability of the anion to approach the positively charged positions (steric effects due to molecular shape) are the determining factors in deciding the amount of ion pairing. DFT calculations of the charges in four salts of type 1, as well as in a variety of other salts, using a natural population analysis (NPA), support this view. This represents the first attempt, using experimental data, to understand, correlate, and partially explain the various degrees of ion pairing in a widely different collection of salts.
Asunto(s)
Espectroscopía de Resonancia Magnética , Cloruro de Metileno/química , Compuestos de Rutenio/química , Sales (Química)/química , Elementos de Transición/química , Difusión , Modelos MolecularesRESUMEN
Five pure and four hybrid DFT functionals associated with VDZP, VTZP, and VQZP basis sets are tested (Gaussian 03) for their performance on the geometry optimization of [Ru(η(5)-C5H5)(η(3)-CH2CHCHC6H5)(CH3CN)2](2+). When the calculated geometries were compared with the X-ray structure determination for the analogous complex with permethylated cyclopentadienyl, it was found that in all cases the coordination mode of the η(3)-allyl was very poorly described, despite the functional used. The Ru-C bond distance corresponding to the substituted allyl carbon was overestimated by 0.23-0.50 Å, depending on the functional and the basis set used. These results were reproduced by further testing carried out with the ADF program and larger basis sets. MP2 leads to an acceptable value for the same Ru-C distance, with an underestimation of 0.07 Å, suggesting that, at least in the case of the functionals tested, DFT does not provide an accurate description of a weak Ru-C interaction.
RESUMEN
In non-competitive solvents, the tris(3-ureidobenzyl)amines 1 a-c form dimeric assemblies in which guests such as CH(3)CN, CH(3)NO(2), CH(2)Cl(2), CH(3)I, CH(2)BrCl, CH(2)Br(2), CHCl(3) and C(6)H(6) can be encapsulated. Variable temperature (1)H and (1)H,(1)H-ROESY NMR spectroscopy, as well as pulsed-gradient spin-echo (PGSE) diffusion measurements were used to investigate the encapsulation within 1 a1 a (1 a: tris{3-[N'-(4-butylphenyl)ureido]benzyl}amine). Kinetic parameters for the encapsulation of CH(3)NO(2), CH(2)Cl(2) and CH(3)I, both in CDCl(3) and in [D(8)]toluene have been obtained by using magnetisation transfer methods. These data are discussed together with the thermodynamic parameters. The affinity between guest and capsule seems to be dictated mainly by the electronic, size and shape complementarity between cavity and guest. A gating mechanism for guest exchange is proposed.
RESUMEN
A series of ruthenium hydride N-alkyl heterocyclic carbene complexes has been investigated as catalysts for a tandem oxidation/Wittig/reduction reaction to give C-C bonds from alcohols. The C-H-activated carbene complex Ru(IiPr(2)Me(2))'(PPh(3))(2)(CO)H (9) proves to be the most active precursor catalyzing the reaction of PhCH(2)OH and Ph(3)P=CHCN in 3 h at 70 degrees C. These results provide (a) a rare case in which N-alkyl carbenes afford higher catalytic activity than their N-aryl counterparts and (b) a novel example of the importance of NHC C-H activation in a catalytic cycle.
RESUMEN
THF solutions of the cationic chiral 1,3-diphenylallyl bidentate phosphine complexes [Pd(eta(3)-PhCHCHCHPh)(Duphos)](CF(3)SO(3)), Duphos = 1,2-Bis-((2R,5R)-2,5-dimethylphospholano)benzene), 2, and [Pd(eta(3)-PhCHCHCHPh)(P,S)]BF(4), 4, P,S = [8-((o-(diphenylphosphino)benzyl) thiomethyl]-(7,7'-dimethyl)-exo-norborneol, have been studied via pulsed gradient spin-echo (PGSE) diffusion, (1)H, (19)F HOESY and a variety of other multi-dimensional NMR methods. On the basis of the (1)H, (19)F HOESY data, the anions show a preference for a specific structural position with respect to the eta(3)-PhCHCHCHPh allyl ligand, i.e. the anion does not move evenly around the periphery of the cation. THF is shown to promote significant ion pairing, although neither 2 nor 4 shows 100% ion pairing.
Asunto(s)
Compuestos Alílicos/química , Furanos/química , Compuestos Organometálicos/química , Paladio/química , Compuestos Alílicos/clasificación , Cationes , Difusión , Flúor/química , Hidrógeno/química , Espectroscopía de Resonancia Magnética/métodos , Estructura Molecular , Compuestos Organometálicos/clasificación , Paladio/clasificación , Fosfinas/química , Soluciones/químicaRESUMEN
Compounds formed by linking two tris(ureidobenzyl)amine modules with a hexamethylene tether are described. These compounds self-assemble to form bicapsular aggregates featuring two rings of six hydrogen-bonded ureas. (1)H and (1)H/(1)H ROESY NMR spectroscopy, together with pulsed gradient spin echo (PGSE) NMR diffusion measurements, have been used to characterize the dimers in solution. The results have been compared with energy-minimized structures. The new compounds are kinetically stable on the NMR timescale, and their thermodynamic stabilities are comparable to other capsular aggregates derived from tris(ureidobenzyl)amines.