Ultrasensitive anion detection by NMR spectroscopy: a supramolecular strategy based on modulation of chemical exchange rate.

NMR spectroscopy is a powerful tool for monitoring molecular interactions and is widely used to characterize supramolecular systems at the atomic level. NMR is limited for sensing purposes, however, due to low sensitivity. Dynamic processes such as conformational changes or binding events can induce drastic effects on NMR spectra in response to variations in chemical exchange (CE) rate, which can lead to new strategies in the design of supramolecular sensors through the control and monitoring of CE rate. Here, we present an indirect NMR anion sensing technique in which increased CE rate, due to anion-induced conformational flexibility of a relatively rigid structure of a novel sensor, allows ultrasensitive anion detection as low as 120 nM.

Synthesis and characterization of iron(II) complexes with tetradentate diiminodiphosphine or diaminodiphosphine ligands as precatalysts for the hydrogenation of acetophenone.

Six complexes of the type trans-[Fe(NCMe)2(P-N-N-P)]X2 (X = BF4(-), B{Ar(f)}4(-)) (Ar(f) = 3,5-(CF3)2C6H3) containing diiminodiphosphine ligands and the complexes trans-[Fe(NCMe)2(P-NH-NH-P)][BF4]2 with a diaminodiphosphine ligand were obtained by the reaction of Fe(II) salts with achiral and chiral P-N-N-P or P-NH-NH-P ligands, respectively, in acetonitrile at ambient temperature. The P-N-N-P ligands are derived from reaction of ortho-diphenylphosphinobenzaldehyde with the diamines 1,2-ethylenediamine, 1,3-propylenediamine, (S,S)-1,2-disopropyl-1,2-diaminoethane, and (R,R)-1,2-diphenyl-1,2-diaminoethane. Some complexes could also be obtained for the first time in a one-pot template synthesis under mild reaction conditions. Single crystal X-ray diffraction studies of the complexes revealed a trans distorted octahedral structure around the iron. The iPr or Ph substituents on the diamine were found to be axial in the five-membered Fe-N-CHR-CHR-N- ring of the chiral P-N-N-P ligands. A steric clash between the imine hydrogen and the substituent probably determines this stereochemistry. The diaminodiphosphine complex has longer Fe-N and Fe-P bonds than the analogous diiminodiphosphine complex. The new iron compounds were used as precatalysts for the hydrogenation of acetophenone. The complexes without axial substituents on the diamine had moderate catalytic activity while that with axial Ph substituents had low activity but fair (61%) enantioselectivity for the asymmetric hydrogenation of acetophenone. The fact that the diaminodiphosphine complex has a slightly higher activity than the corresponding diiminodiphosphine complex suggests that hydrogenation of the imine groups in the P-N-N-P ligand may be important for catalyst activation. Evidence is provided, including the first density-functional theory calculations on iron-catalyzed outer-sphere ketone hydrogenation, that the mechanism is similar to that of ruthenium analogues.

Syntheses, structures, and reactivities of novel palladium beta-diiminato-acetate complexes.

The reaction between (Ar(2)nacnac)H (Ar = C(6)H(5), ligand a; 2,6-((i)Pr)(2)C(6)H(3), ligand b) and [Pd(OAc)(2)] produces red complexes [Pd(Ar(2)nacnac)(OAc)] (1a: Ar = C(6)H(5); 1b: Ar = 2,6-((i)Pr)(2)C(6)H(3)). Complex 1a has a dimeric structure in the solid state with two bridging acetates, while a monomer-dimer equilibrium establishes in solution. Complex 1b is monomeric in both the solid state and solution. Both are air- and moisture-stable compounds, unlike [Pd(Ph(2)nacnac)(2)] (2), which easily hydrolyzes in the presence of moisture to give [Pd(Phnacac)(2)] (3) (Phnacac = {CH(3)C(NPh)CHC(O)CH(3)}(-)). Compound 1a reacts with metal acetates to produce heterotrimetallic complexes of a general formula [Pd(Ph(2)nacnac)](2)-mu-[M(OAc)(4)] (4, M = Cu; 5, M = Zn). Treating 1a with KOH in THF, or alternatively [Pd(Ph(2)nacnac)Cl](2) with KO(t)Bu in wet THF, produces [Pd(Ph(2)nacnac)(OH)](2) (6).

Novel dinuclear and trinuclear palladium beta-diiminate complexes containing amido-chloro double-bridges.

We report the formation of an unexpected trinuclear palladium beta-diiminate complex from the decomposition of [Pd(Ph(2)nacnac)(Cl)(4-H(2)NC(6)H(4)-(t)Bu)] (nacnac = beta-diiminate derived from acetylacetone), the proposed reaction pathway, and the synthesis of the first dinuclear palladium complex with an amido-chloro double-bridge.

Novel hydrido-ruthenium(II) complexes with histidine derivatives and their application in the hydrogenation of ketones.

The complexes RuHCl((R)-binap)(L-NH2) with L-NH2 = (S)-histidine-Me-ester (1), histamine (3), (S)-histidinol (4) or 1-Me-(S)-histidine-Me-ester (5), and RuHCl((S)-binap)(L-NH(2)) with L-NH2 = (S)-histidine-Me-ester (2) have been prepared in 60-81% overall yields in a one-pot, three-step procedure from the precursor RuCl2(PPh3)3. Their octahedral structures with hydride trans to chloride were deduced from their NMR spectra and confirmed by the results of a single crystal X-ray diffraction study for complex 3. Under H2 and in the presence of KOtBu, complexes 1-5 in 2-propanol form moderately active catalyst precursors for the asymmetric hydrogenation of acetophenone to 1-phenylethanol. Complex 5 is more active and enantioselective than complexes 1-4, allowing complete conversion to 1-phenylethanol in 46% e.e. (R) in 72 h at 20 degrees C under 1 MPa of H2 with substrate : catalyst : base = 2000 : 1 : 30. Complex 5, when activated, also catalyzes the hydrogenation of trans-4-phenyl-3-buten-2-one to exclusively the allyl alcohol 4-phenyl-3-buten-2-ol under 2.7 MPa of H2 at 50 degrees C in 2-propanol. This selectivity for C=O versus C=C hydrogenation is consistent with a mechanism involving the outer sphere transfer of hydride and proton to the polar bond. Further extensions to complexes with peptides with N-terminal histidine groups appear feasible on the basis of the current work.

Chemistry of ruthenium(II) monohydride and dihydride complexes containing pyridyl donor ligands including catalytic ketone H2-hydrogenation.

In this study we determine the changes to the properties of dihydride catalysts for ketone H2-hydrogenation by successively replacing the amine donors in the known dach complex RuH2(PPh3)2(dach) (2a), dach = 1,2-(R,R)-diaminocyclohexane, with one pyridyl group in the corresponding 2-(aminomethyl)pyridine (ampy) complexes RuH2(PPh3)2(ampy) (2b) and with two pyridyl groups in the complexes RuH2(PPh3)2(bipy) (2c) and RuH2(PPh3)2(phen) (2d). The ruthenium monohydride complex, (OC-6-54)-RuHCl(PPh3)2(ampy), (1b with Cl trans to H) was prepared by the addition of 1 equiv of ampy to RuHCl(PPh3)3 in THF. Treatment of the monohydride complex with K[BH(sec-Bu)3] in THF or KOtBu/H2 in toluene resulted in the formation of a mixture of at least two isomers of the highly reactive, air-sensitive ruthenium dihydride complex 2b. One is the cis dihydride (OC-6-14)-2b or more simply c,t-2b with trans PPh3 groups and another is the cis dihydride c,c-2b (OC-6-42) that has PPh3 trans to H and PPh3 trans to N(pyridyl). The isomer c,c-2b slowly converts to c,t-2b in solution. The reaction of 1b with KOtBu under Ar results in the formation of a mixture that includes a complex with an imino ligand HN=CH-2-py while the same reaction under H2 leads to c,c-2b and then c,t-2b. The dach complex c,t-2a, reacts with ampy, 2,2'-bipyridine (bipy), and 1,10-phenanthroline (phen) in refluxing THF to form the substituted cis-dihydride complexes c,t-2b, (OC-6-13)-RuH2(PPh3)2(bipy) (c,t-2c with trans PPh3 groups) and (OC-6-13)-RuH2(PPh3)2(phen), c,t-2d, respectively. The dihydrides containing amino groups and cis-PPh3 groups, i.e., c,c-2a or c,c-2b, are active precatalysts for the H2-hydrogenation of acetophenone (neat or in benzene) under mild reaction conditions, whereas those with trans-PPh3 groups, c,t-2a and c,t-2b are much less active. The combination of ampy complex 1b and KOtBu also provides a catalyst in benzene that is more active than the corresponding dach system. The complexes without amino groups c,t-2c and c,t-2d are air-stable and inactive as hydrogenation catalysts under comparable conditions. The mechanism of hydrogenation of ketones catalyzed by isomers of 2a,b is thought to be similar and to proceed via a trans-dihydride complex, t,c-2a or t,c-2b, and an amido complex, neither of which are directly observed for the ampy complexes. The dihydride complex c,t-2b reacts with formic acid to give (OC-6-45)-RuH(OCHO)(PPh3)2(ampy), 3b, with formate trans to hydride. The structures of 1b, c,t-2b, c,t-2c, and 3b have been determined by single-crystal X-ray diffraction.

A succession of isomers of ruthenium dihydride complexes. Which one is the ketone hydrogenation catalyst?

Reaction of RuHCl(PPh(3))(2)(diamine) (1a, diamine = (R,R)-1,2-diaminocyclohexane, (R,R)-dach; 1b, diamine = ethylenediamine, en) with KO(t)Bu in benzene quickly generates solutions of the amido-amine complexes RuH(PPh(3))(2)(NHC(6)H(10)NH(2)), (2a'), and RuH(PPh(3))(2)(NHCH(2)CH(2)NH(2)), (2b'), respectively. These solutions react with dihydrogen to first produce the trans-dihydrides (OC-6-22)-Ru(H)(2)(PPh(3))(2)(diamine) (t,c-3a, t,c-3b). Cold solutions (-20 degrees C) containing trans-dihydride t,c-3a react with acetophenone under Ar to give (S)-1-phenylethanol (63% ee). Complexes t,c-3 have lifetimes of less than 10 min at 20 degrees and then isomerize to the cis-dihydride, cis-bisphosphine isomers (OC-6-32)-Ru(H)(2)(PPh(3))(2)(diamine) (Delta/Lambda-c,c-3a, c,c-3b). A solution containing mainly Delta/Lambda-c,c-3a reacts with acetophenone under Ar to give (S)-1-phenylethanol in 20% ee, whereas it is an active precatalyst for its hydrogenation under 5 atm H(2) to give 1-phenylethanol with an ee of 50-60%. Complexes c,c-3 isomerize to the cis-dihydride, trans-bisphosphine complexes (OC-6-13)-Ru(H)(2)(PPh(3))(2)(diamine) (c,t-3a, c,t-3b) with half-lives of 40 min and 1 h, respectively. A mixture of Delta/Lambda-c,c-3a and c,t-3a can also be obtained by reaction of 1a with KBH(Bu(sec))(3). A solution of complex c,t-3a in benzene under Ar reacts very slowly with acetophenone. These results indicate that the trans-dihydrides t,c-3a or t,c-3b along with the corresponding amido-amine complexes 2a' or 2b' are the active hydrogenation catalysts in benzene, while the cis-dihydrides c,c-3a or c,c-3b serve as precatalysts. The complexes RuCl(2)(PPh(3))(2)((R,R)-dach) or 1a, when activated by KO(t)Bu, are also sources of the active catalysts. A study of the kinetics of the hydrogenation of acetophenone in benzene catalyzed by 3a indicates a rate law: rate = k[c,c-3a](initial)[H(2)] with k = 7.5 M(-1) s(-1). The turnover-limiting step appears to be the reaction of 2a' with dihydrogen as it is for RuH(NHCMe(2)CMe(2)NH(2))(PPh(3))(2) (2c'). The catalysts are more active in 2-propanol, even without added base, and the kinetic behavior is complicated. The basic cis-dihydride c,t-3a reacts with [NEt(3)H]BPh(4) to produce the dihydrogen complex (OC-14)-[Ru(eta(2)-H(2))(H)(PPh(3))(2)((R,R)-dach)]BPh(4) (4) and with diphenylphosphinic acid to give the complex RuH(O(2)PPh(2))(PPh(3))(2)((R,R)-dach) (5). The structure of 5 models aspects of the transition state structure for the ketone hydrogenation step. Complex 2b' decomposes rapidly under Ar to give dihydrides 3b along with a dinuclear complex (PPh(3))(2)HRu(mu-eta(2);eta(4)-NHCHCHNH)RuH(PPh(3))(2) (6) containing a rare, bridging 1,4-diazabutadiene group. The formation of an imine by beta-hydride elimination from the amido-amine ligand of 2a' under Ar might explain some loss of enantioselectivity of the catalyst. The structures of complexes 1a, 5, and 6 have been determined by single-crystal X-ray diffraction.

Mechanism of the hydrogenation of ketones catalyzed by trans-dihydrido(diamine)ruthenium II complexes.

The complexes trans-RuH(Cl)(tmen)(R-binap) (1) and (OC-6-43)-RuH(Cl)(tmen)(PPh(3))(2) (2) are prepared by the reaction of the diamine NH(2)CMe(2)CMe(2)NH(2) (tmen) with RuH(Cl)(PPh(3))(R-binap) and RuH(Cl)(PPh(3))(3), respectively. Reaction of KHB(sec)Bu(3) with 1 yields trans-Ru(H)(2)(R-binap)(tmen) (5) while reaction of KHB(sec)Bu(3) or KO(t)Bu with 2 under Ar yields the new hydridoamido complex RuH(PPh(3))(2)(NH(2)CMe(2)CMe(2)NH) (4). Complex 4 has a distorted trigonal bipyramidal geometry with the amido nitrogen in the equatorial plane. Loss of H(2) from 5 results in the related complex RuH(R-binap)(NH(2)CMe(2)CMe(2)NH) (3). Reaction of H(2) with 4 yields the trans-dihydride (OC-6-22)-Ru(H)(2)(PPh(3))(2)(tmen)(6). Calculations support the assignment of the structures. The hydrogenation of acetophenone is catalyzed by 5 or 4 in benzene or 2-propanol without the need for added base. For 5 in benzene at 293 K over the ranges of concentrations [5] = 10(-)(4) to 10(-)(3) M, [ketone] = 0.1 to 0.5 M, and of pressures of H(2) = 8 to 23 atm, the rate law is rate = k[5][H(2)] with k = 3.3 M(-1) s(1), DeltaH++ = 8.5 +/- 0.5 kcal mol(-1), DeltaS++ = -28 +/- 2 cal mol(-1) K(-1). For 4 in benzene at 293 K over the ranges of concentrations [4] = 10(-4) to 10(-3) M, [ketone] 0.1 to 0.7 M, and of pressures of H(2) = 1 to 6 atm, the preliminary rate law is rate = k[4][H(2)] with k = 1.1 x 10(2) M(-1) s(-1), DeltaH++ = 7.6 +/- 0.3 kcal mol(-1), DeltaS++ = -23 +/- 1 cal mol(-1) K(-1). Both theory and experiment suggest that the intramolecular heterolytic splitting of dihydrogen across the polar Ru=N bond of the amido complexes 3 and 4 is the turn-over limiting step. A transition state structure and reaction energy profile is calculated. The transfer of H(delta+)/H(delta-) to the ketone from the RuH and NH groups of 5 in a Noyori metal-ligand bifunctional mechanism is a fast process and it sets the chirality as (R)-1-phenylethanol (62-68% ee) in the hydrogenation of acetophenone. The rate of hydrogenation of acetophenone catalyzed by 5 is slower and the ee of the product is low (14% S) when 2-propanol is used as the solvent, but both the rate and ee (up to 55% R) increase when excess KO(t)Bu is added. The formation of ruthenium alkoxide complexes in 2-propanol might explain these observations. Alkoxide complexes [RuP(2)]H(OR)(tmen), [RuP(2)] = Ru(R-binap) or Ru(PPh(3))(2), R= (i) Pr, CHPhMe, (t)Bu, are observed by reacting the alcohols (i)PrOH, phenylethanol, and (t)BuOH with the dihydrides 5 and 6, respectively, under Ar. In the absence of H(2), the amido complexes 3 and 4 react with acetophenone to give the ketone adducts [RuP(2)]H(O=CPhMe)(NH(2)CMe(2)CMe(2)NH) in equilibrium with the enolate complexes trans- [RuP(2)](H)(OCPh=CH(2))(tmen) and eventually the decomposition products [RuP(2)]H(eta(5)-CH(2)CPhCHCPhO), with the binap complex characterized crystallographically. In general, proton transfer from the weakly acidic molecules dihydrogen, alcohol, or acetophenone to the amido nitrogen of complexes 3 and 4 is favored in two ways when the molecule coordinates to ruthenium: (1) an increase in acidity of the molecule by the Lewis acidic metal and (2) an increase in the basicity of the amido nitrogen caused by its pyramidalization. The formato complexes trans-[RuP(2)]H(OCHO)(tmen) were prepared by reacting the respective complex 4 or 5 with formic acid. The crystal structure of RuH(OCHO)(PPh(3))(2)(tmen) displays similar features to the calculated transition state for H(delta+)/H(delta-) transfer to the ketone in the catalytic cycle.