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Time-gated pulsed glow discharge: real-time chemical speciation at the elemental, structural, and molecular level for gas chromatography time-of-flight mass spectrometry.

A millisecond pulsed glow discharge is used as a versatile ion source for time-gated generation of elemental, structural, and molecular ions. The utility of this ion source for comprehensive chemical analysis of a series of aromatic and halogenated hydrocarbons is illustrated in this manuscript. To highlight the analytical utility of this transient ion source, it was connected to a gas chromatograph for the mass spectrometric determination of mixtures containing benzene, toluene, o-xylene, cymene, tert-butylbenzene, carbon tetrachloride, chloroform, chlorobenzene, tetrachlorethane, and dichlorobenzene. Explicit chemical analysis was accomplished by introducing the GC eluent into a pulsed glow discharge operating at a rate of 100 Hz with a 50% duty cycle. Using three independent digitizers for time-gated acquisition in three separate time regimes, nearly concurrent collection of elemental, structural, and molecular information was accomplished. In general, elemental information was obtained during the first 0.015 ms after the plasma onset; structural information, as ascertained from molecular fragmentation, was obtained during the plateau time regime when the plasma pulse is at a steady state, whereas molecular M(+) and MH(+) ions were obtained during the afterpeak time regime, that is, after the cessation of the plasma power pulse.

Journal Article↗

Treatment of volatile organic chemicals on the EPA Contaminant Candidate List using ozonation and the O3/H2O2 advanced oxidation process.

Seven volatile organic chemicals (VOCs) on the EPA Contaminant Candidate List together with 1,1-dichloropropane were studied for their reaction kinetics and mechanisms with ozone and OH radicals during ozonation and the ozone/ hydrogen peroxide advanced oxidation process (O3/H2O2 AOP) using batch reactors. The three aromatic VOCs demonstrated high reactivity during ozonation and were eliminated within minutes after ozone addition. The high reactivity is attributed to their fast, indirect OH radical reactions with k(OH,M) of (5.3-6.6) x 10(9) M(-1) s(-1). Rates of aromatic VOC degradation are in the order 1,2,4-trimethylbenzene > p-cymene > bromobenzene. This order is caused by the selectivity of the direct ozone reactions (k(O3,M) ranges from 0.16 to 304 M(-1) s(-1)) and appears to be related to the electron-donating or -withdrawing ability of the substituent groups on the aromatic ring. The removal rates for the five aliphatic VOCs are much lower and are in the order 1,1-dichloropropane > 1,3-dichloropropane > 1,1-dichloroethane > 2,2-dichloropropane > 1,1,2,2-tetrachloroethane. The second-order indirect rate constants for the aliphatic VOCs range from 0.52 x 10(8) to 5.5 x 10(8) M(-1) s(-1). The relative stability of the carbon-centered intermediates seems to be related to the relative reactivity of the aliphatic VOCs with OH radicals. Except for 1,3-dichloropropane, ozonation and the O3/H2O2 AOP are not effective for the removal of other aliphatic VOCs. Bromide formation during the ozonation of bromobenzene indicates that bromate can be formed, and thus, ozonation and O3/H2O2 AOP may not be suitable for the treatment of bromobenzene.

Hydrocarbons↗

Stabilization of molecular LiF and LiFHF inside metallamacrocyclic hosts.

Complexes of molecular LiF and LiFHF were synthesized using the metallamacrocyclic receptors [(cymene)Ru(C(5)H(3)NO(2))](3) (1), [CpRh(C(5)H(3)NO(2))](3) (2), and [CpIr(C(5)H(3)NO(2))](3) (3). LiBF(4) complexes of 1-3 were prepared and subsequently treated with F(-) or FHF(-) to give the desired products in an anion-exchange reaction. All complexes were characterized by multinuclear NMR spectroscopy ((1)H, (13)C, (19)F, (7)Li). Strong scalar coupling between (7)Li and (19)F is observed for the LiF and the LiFHF complexes ((1)J(LiF) = 91-103 Hz). The LiFHF adduct of 1 displays fluxional behavior with fast exchange of the two fluorine atoms. The structures of the complexes 1.LiBF(4), 2.LiBF(4), 1.LiF, 2.LiF, 1.LiFHF, and 3.LiFHF were determined by single-crystal X-ray analysis. Li-F bond lengths between 1.77 and 1.81 A were found. The LiFHF complexes show a hydrogen difluoride anion coordinated in a bent fashion via one fluorine atom to the lithium ion.

Journal Article↗

Electronic effects in 12-metallacrown-3 complexes. A theoretical and experimental study.

The Mulliken charges of the 12-metallacrown-3 complex [(C(6)H(6))Ru(C(5)H(3)NO(2))](3) were determined by a single point analysis at the HF level. For comparison, a Mulliken population analysis was carried out for the organic analogue 12-crown-3. The partial negative charges on the O-donor atoms of the metallamacrocycle were found to be larger than those on the O-donor atoms of 12-crown-3. The 12-metallacrown-3 complex [(cymene)Ru(C(5)H(2)ClNO(2))](3) with chloro-substituents in position 5 of the pyridonate ligand was synthesized to determine the effect of electron withdrawing groups on the structure and the host-guest properties of the receptor. The chloro-substituents were found to have only a small influence on the structures, but they reduce the binding affinity for LiCl and NaCl by approximately 2 orders of magnitude.

Journal Article↗

PGSE and NOE NMR evidence for higher order aggregation in some cationic ruthenium complexes in both protic and aprotic solvents.

PGSE and NOE NMR measurements were carried out for complexes [Ru(eta(6)-cymene)((2-R-C(6)H(4))N=C(Me)-C(Me)=N(2-R-C(6)H(4)))Cl]X (X = BF(4) or BPh(4)) in both protic and aprotic solvents with a relative permettivity (epsilon(r)) ranging from 2.27 (benzene-d(6)) to 46.45 (dimethyl sulfoxide-d(6)). PGSE and NOE results indicate that complexes have a tendency to aggregate even in medium-polarity solvents such as ethanol (epsilon(r) = 24.55) and methanol (epsilon(r) = 32.66). In addition, the aggregation process is favored by a decrease of epsilon(r) and, unexpectedly, by protic solvents. NOE measurement investigations, interpreted with the help of theoretical calculations and confirmed by X-ray single crystal studies, suggest different aggregation processes for the two counteranions: two cationic moieties approach each other when X = BF(4) while the anion bridges two cationic moieties when X = BPh(4).

Journal Article↗

Synthesis and reactivity of new chelate-N-heterocyclic biscarbene complexes of ruthenium.

The carbene-ligand precursors methylenebis(N-alkylimidazolium) iodide (alkyl = methyl, neo-pentyl) and ethylenebis(N-methylimidazolium) chloride have been used in the preparation of several new Ru(II)-p-cymene complexes where the ligand behaves as mono- and bidentate. The molecular structures of the two biscarbene-complexes are reported. From the data reported, we can conclude that steric reasons (mainly the bisimidazolium linkers, methylene/ethylene) are the main factors determining both reactivity and synthetic difficulties of the products reported.

Journal Article↗

Diastereoselective formation of metallamacrocyclic (arene)Ru(II) and CpRh(III) complexes.

The reaction of [(arene)RuCl(2)](2) (arene = cymene, 1,3,5-C(6)H(3)Me(3)) and [CpRhCl(2)](2) half-sandwich complexes with tridentate heterocyclic ligands in the presence of base has been investigated. In all cases, the chloro-ligands were substituted to give metallacyclic products with ring sizes between 4 and 18 atoms. The cyclization occurs in a highly diastereoselective fashion with chiral recognition between the different metal fragments. The complexes were comprehensively characterized by elemental analysis, NMR spectroscopy, and single crystal X-ray crystallography. For 2-hydroxy-nicotinic acid and 2-amino-nicotinic acid, dinuclear structures were obtained (15-17) whereas for 2,3-dihydroxyquinoline, 2,3-dihydroxyquinoxaline, and 6-methyl-2,3-phenazinediol, trimeric assemblies were found (19-22), and for 4-imidazolecarboxylic acid, a tetrameric assembly (18) was found.

Journal Article↗

Luminescent piano-stool complexes incorporating 1-(4-cyanophenyl)imidazole: synthesis, spectral, and structural studies.

Three novel luminescent piano-stool arene ruthenium complexes of general formula [(eta(6)-arene)RuCl(2)(CPI)] (eta(6)-arene = benzene, 1, p-cymene, 2, and hexamethylbenzene, 3; CPI=1-(4-cyanophenyl)imidazole were prepared. The molecular structures of 2 and 3 were determined crystallographically. Reaction of 1-3 with EPh(3) (E = P, As, or Sb) and N-N donor bases such as 2,2'-bipyridine and 1,10-phenanthroline afforded cationic mononuclear complexes of general formula [(eta(6)-arene)RuCl(CPI)(EPh(3))](+) (eta(6)-arene = C(6)H(6), E = P (1a), E = As (1b), E = Sb(1c); eta(6)-arene = C(10)H(14), E = P (2a), E = As (2b), E = Sb (2c); eta(6)-arene = C(6)Me(6), E = P (3a), E = As (3b), E = Sb (3c)) and [(eta(6)-arene)Ru(N-N)(CPI)](2+) (eta(6)-arene = C(6)H(6), N-N = bipy (1d), N-N = phen (1e); eta(6)-arene = C(10)H(14), N-N = bipy (2d), N-N = phen (2e); eta(6)-arene = C(6)Me(6), N-N = bipy (3d), N-N = phen (3e)). Molecular structures of 1a and 2a were also confirmed by X-ray crystallography. Structural studies of the complexes 2, 3, 1a, and 2a supported coordination of CPI through the imidazole nitrogen and the presence of a pendant nitrile group. Structural data also revealed stabilization of crystal packing in the complexes 2, 3, and 2a by C-H...X (X = Cl, F) type inter- and intramolecular interactions and in complex 1a by pi-pi stacking. Moreover, neutral homonuclear bimetallic complexes 2f,g were prepared by using complex 2 as a metallo-ligand, where CPI acts as a bridge between two metal centers. Emission spectra of the mononuclear complexes [(eta(6)-arene)RuCl(2)(CPI)] and its derivatives exhibited intense luminescence when excited in the metal to ligand charge-transfer band.

Journal Article↗

Amphiphilic ruthenium sensitizers and their applications in dye-sensitized solar cells.

Amphiphilic ligands 4,4'-bis(1-adamantyl-aminocarbonyl)-2,2'-bipyridine (L(1)), 4,4'-bis[5-[N-[2-(3beta-cholest-5-en-3-ylcarbamate-N-yl)ethyl]aminocarbonyl]]-2,2'-bipyridine (L(2)), 4,4'-bis[5-[N-[2-(3beta-cholest-5-en-3-ylcarbamate-N-yl)propyl]aminocarbonyl]]-2,2'-bipyridine (L(3)), and 4,4'-bis(dodecan-12-ol)-2,2'-bipyridine (L(4)) and their heteroleptic ruthenium(II) complexes of the type [Ru(II)LL(1)(NCS)(2)] (5), [Ru(II)LL(2)(NCS)(2)] (6), [Ru(II)LL(3)(NCS)(2)] (7), and [Ru(II)LL(4)(NCS)(2)] (8) (where L = 4,4'-bis(carboxylic acid)-2,2'-bipyridine) have been synthesized starting from dichloro(p-cymene)ruthenium(II) dimer. All the ligands and the complexes were characterized by analytical, spectroscopic, and electrochemical techniques. The performance of these complexes as charge-transfer photosensitizers in nanocrystalline TiO(2)-based solar cells was studied. When complexes 5-8 anchored onto a 12 + 4 microm thick nanocrystalline TiO(2) films, very efficient sensitization was achieved (85 +/- 5% incident photon-to-current efficiencies in the visible region, using an electrolyte consisting of 0.6 M butylmethylimidazolium iodide, 0.05 M I(2), 0.1 M LiI, and 0.5 M tert-butyl pyridine in 1:1 acetonitrile + valeronitrile). Under standard AM 1.5 sunlight, the complex 8 yielded a short-circuit photocurrent density of 17 +/- 0.5 mA/cm(2), the open-circuit voltage was 720 +/- 50 mV, and the fill factor was 0.72 +/- 0.05, corresponding to an overall conversion efficiency of 8.8 +/- 0.5%.

Journal Article↗

195Pt NMR of heteropolymetallic complexes containing secondary dithiooxamides as binucleating ligands.

Monometallic [Pt{S-S2C2(NR)2H}2] (S-S2C2(NR)2H = kappa2-S,S-S2C2(NR)2H = bis-dialkyl-dithioxamidate, R = methyl, isoamyl, benzyl) and binuclear and trinuclear heterobimetallic complexes [Pt{S-S2C2(NR)2H}{mu-S2C2(NR)2}MLn] (mu-S2C2(NR)2 = kappa2-S,S(Pt)-kappa2-N,N(M)-S2C2(NR)2) and [Pt{{mu-S2C2(NR)2}MLn}2] (MLn+ = [(eta3-allyl)palladium]+, [bis-(2-phenylpyridine)rhodium]+, [(eta6-p-cymene)(chloro)ruthenium]+, [(1,4-cyclooctadiene)rhodium]+, [(pentamethylcyclopentadienyl)(chloro)rhodium]+) have been prepared and characterized. The progressive substitution of the residual amidic hydrogen in the [Pt{S-S2C2(NR)2H}2] complexes with a MLn+ metal fragment results in the deshielding of platinum nuclei, a red shift of the MLCT absorption maximum, and a decrease in the oxidation potential. Such behavior has been interpreted as a progressive electron shift from platinum to the binucleating ligands, the extent of which depends on the nature of MLn+ metal fragment.

Journal Article↗

Cyclodiphosphazanes with hemilabile ponytails: synthesis, transition metal chemistry (Ru(II), Rh(I), Pd(II), Pt(II)), and crystal and molecular structures of mononuclear (Pd(II), Rh(I)) and bi- and tetranuclear rhodium(I) complexes.

Cyclodiphosphazanes having hemilabile ponytails such as cis-[(t)()BuNP(OC(6)H(4)OMe-o)](2) (2), cis-[(t)()BuNP(OCH(2)CH(2)OMe)](2) (3), cis-[(t)BuNP(OCH(2)CH(2)SMe)](2) (4), and cis-[(t)BuNP(OCH(2)CH(2)NMe(2))](2) (5) were synthesized by reacting cis-[(t)()BuNPCl](2) (1) with corresponding nucleophiles. The reaction of 2 with [M(COD)Cl(2)] afforded cis-[MCl(2)(2)(2)] derivatives (M = Pd (6), Pt (7)), whereas, with [Pd(NCPh)(2)Cl(2)], trans-[MCl(2)(2)(2)] (8) was obtained. The reaction of 2 with [Pd(PEt(3))Cl(2)](2), [{Ru(eta(6)-p-cymene)Cl(2)](2), and [M(COD)Cl](2) (M = Rh, Ir) afforded mononuclear complexes of Pd(II) (9), Ru(II) (11), Rh(I) (12), and Ir(I) (13) irrespective of the stoichiometry of the reactants and the reaction condition. In the above complexes the cyclodiphosphazane acts as a monodentate ligand. The reaction of 2 with [PdCl(eta(3)-C(3)H(5))](2) afforded binuclear complex [(PdCl(eta(3)-C(3)H(5)))(2){((t)BuNP(OC(6)H(4)OMe-o))(2)-kappaP}] (10). The reaction of ligand 3 with [Rh(CO)(2)Cl](2) in 1:1 ratio in CH(3)CN under reflux condition afforded tetranuclear rhodium(I) metallamacrocycle (14), whereas the ligands 4 and 5 afforded bischelated binuclear complexes 15 and 16, respectively. The crystal structures of 8, 9, 12, 14, and 16 are reported.

Journal Article↗

Diastereospecific and diastereoselective syntheses of Ruthenium(II) complexes using N,N' bidentate ligands aryl-pyridin-2-ylmethyl-amine ArNH-CH2-2-C5H4N and their oxidation to imine ligands.

Coordination of N,N' bidentate ligands aryl-pyridin-2-ylmethyl-amine ArNH-CH2-2-C5H4N 1 (Ar = 4-CH3-C6H4, 1a; 4-CH3O-C6H4, 1b; 2,6-(CH3)2-C6H3, 1c; 4-CF3-C6H4, 1d) to the moieties [Ru(bipy)2]2+, [Ru(eta5-C5H5)L]+ (L = CH3CN, CO), or [Ru(eta6-arene)Cl]2+ (arene = benzene, p-cymene) occurs under diastereoselective or diastereospecific conditions. Detailed stereochemical analysis of the new complexes is included. The coordination of these secondary amine ligands activates their oxidation to imines by molecular oxygen in a base-catalyzed reaction and hydrogen peroxide was detected as byproduct. The amine-to-imine oxidation was also observed under the experimental conditions of cyclic voltammetry measurements. Deprotonation of the coordinated amine ligands afforded isolatable amido complexes only for the ligand (1-methyl-1-pyridin-2-yl-ethyl)-p-tolyl-amine, 1e, which doesn't contain hydrogen atoms in a beta position relative to the N-H bond. The structures of [Ru(2,2'-bipyridine)2(1b)](PF6)2, 2b; [Ru(2,2'-bipyridine)(2)(1c)](PF6)2, 2c; trans-[RuCl2(COD)(1a)], 3; and [RuCl2(eta6-C6H6)(1a)]PF6, 4a, have been confirmed by X-ray diffraction studies.

Journal Article↗

Facile synthesis of unsymmetrical 9-phospha- and 9-arsafluorenes.

Unsymmetrical 9-chloro-9-phosphafluorenes (dibenzophospholes) and 9-chloro-9-arsafluorenes (dibenzoarsoles) have been obtained by simple thermolysis of m-terphenyldichlorophosphines and -arsines in close to quantitative yields. The reaction temperatures are about 200 degrees C for the phosphines and 140 degrees C for the arsine, and the reactions are complete within 5 min. Alternatively, these compounds can be synthesized through an AlCl3-catalyzed Friedel-Crafts type ring-closure reaction at low temperatures, but this method suffers from difficult workup procedures. The P(As)-Cl functionality is readily alkylated. Methylation of m-xylyl derivative 4 afforded 1-(3,5-dimethylphenyl)-6,8,9-trimethyl-9-phosphafluorene, 11. The latter compound formed the complexes 11 x Fe(CO)4, 12, and 11 x RuCl2(eta(6)-p-cymene), 13, indicating its good donor properties. The new compounds have been characterized by 1H, 13C{1H}, and 31P{1H} NMR spectroscopy; mass spectrometry; and single-crystal X-ray crystallography in the case of 11, 12, and 13.

Journal Article↗

Phenylazo-pyridine and phenylazo-pyrazole chlorido ruthenium(II) arene complexes: arene loss, aquation, and cancer cell cytotoxicity.

Ru(II) eta6-arene complexes containing p-cymene (p-cym), tetrahydronaphthalene (thn), benzene (bz), or biphenyl (bip), as the arene, phenylazopyridine derivatives (C5H4NN:NC6H5R; R = H (azpy), OH (azpy-OH), NMe2 (azpy-NMe2)) or a phenylazopyrazole derivative (NHC3H2NN:NC6H5NMe2 (azpyz-NMe2)) as N,N-chelating ligands and chloride as a ligand have been synthesized (1-16). The complexes are all intensely colored due to metal-to-ligand charge-transfer Ru 4d6-pi* and intraligand pi -->pi* transitions (eta = 5000-63 700 M-1 cm-1) occurring in the visible region. In the crystal structures of [(eta6-p-cym)Ru(azpy)Cl]PF6 (1), [(eta6-p-cym)Ru(azpy-NMe2)Cl]PF6 (5), and [(eta6-bip)Ru(azpy)Cl]PF6 (4), the relatively long Ru-N(azo) and Ru-(arene-centroid) distances suggest that phenylazopyridine and arene ligands can act as competitive pi-acceptors toward Ru(II) 4d6 electrons. The pKa* values of the pyridine nitrogens of the ligands are low (azpy 2.47, azpy-OH 3.06 and azpy-NMe2 4.60), suggesting that they are weak sigma-donors. This, together with their pi-acceptor behavior, serves to increase the positive charge on ruthenium, and together with the pi-acidic eta6-arene, partially accounts for the slow decomposition of the complexes via hydrolysis and/or arene loss (t(1/2) = 9-21 h for azopyridine complexes, 310 K). The pKa* of the coordinated water in [(eta6-p-cym)Ru(azpyz-NMe2)OH2]2+ (13A) is 4.60, consistent with the increased acidity of the ruthenium center upon coordination to the azo ligand. None of the azpy complexes were cytotoxic toward A2780 human ovarian or A549 human lung cancer cells, but several of the azpy-NMe2, azpy-OH, and azpyz-NMe2 complexes were active (IC50 values 18-88 microM).

Antineoplastic Agents↗

Reactions of [(eta(6)-arene)RuCl(2)](2) with Aromatic Phosphines Containing Methoxy Groups in 2,6-Positions.

Reactions of [(eta(6)-arene)RuCl(2)](2) 1 (arene = p-cymene (a), 1,2,3,4-Me(4)C(6)H(2) (b), 1,2,3-Me(3)C(6)H(2) (c)) with tris(2,6-dimethoxyphenyl)phosphine (TDMPP) led to loss of two molecules of CH(3)Cl to give (eta(6)-arene)Ru[{2-O-C(6)H(3)-6-OMe}(2){C(6)H(3)(OMe)(2)-2,6}], 2a-c, which contains a trihapto ligand (eta(3)-P,O,O) derived from TDMPP, whereas the 1,3,5-Me(3)C(6)H(3) (1d), 1,2,3,5-Me(4)C(6)H(2) (1e), and C(6)Me(6) (1f) complexes did not react with TDMPP. The structures of 2a and 2b were confirmed by X-ray analyses: for 2a, a = 11.691(2) Å, b = 15.228(2) Å, c = 10.320(1) Å, alpha = 95.93(1) degrees, beta = 113.783(9) degrees, gamma = 83.86(1) degrees, triclinic, P&onemacr;, Z = 2, R = 0.051; for 2b, a = 17.79(2) Å, b = 15.43(1) Å, c = 20.93(1) Å, beta = 91.25(8) degrees, monoclinic, P2(1)/n, Z = 8, R = 0.056. Bis(2,6-dimethoxyphenyl)phenylphosphine (BDMPP) reacted with 1a, 1b, and 1d at room temperature to give (eta(6)-arene)RuCl[PPh(2-O-C(6)H(3)-6-OMe){C(6)H(3)(OMe)(2)-2,6}], 3a,b,d, which contains a dihapto (eta(2)-P,O) ligand derived from BDMPP by an X-ray analysis of 3a: a = 12.33(1) Å, b = 14.246(8) Å, c = 11.236(9) Å, alpha = 91.47(8) degrees, beta = 117.28(6) degrees, gamma = 111.70(6) degrees, triclinic, P&onemacr;, Z = 2, R = 0.040. A similar reaction with 1f recovered the starting materials, but that in refluxing MeCN produced [(eta(6)-C(6)Me(6))Ru[PPh(2-O-C(6)H(3)-6-OMe}(2)], 4f, containing a trihapto (eta(3)-P,O,O) ligand derived from BDMPP. Complex 1d reacted with BDMPP at reflux in MeCN/CH(2)Cl(2) and resulted in a loss of an arene ring to give a five-coordinate complex, Ru[eta(2)-P,O-PPh(2-O-C(6)H(3)-6-OMe){C(6)H(3)(OMe)(2)-2,6}](2)(MeCN), 5. Treatment of (2,6-dimethoxyphenyl)diphenylphosphine (MDMPP) with 1f gave (eta(6)-C(6)Me(6))RuCl[eta(2)-P,O-PPh(2)(2-O-C(6)H(3)-6-OMe)],6f, and that with 1b gave (eta(6)-1,2,3,4-Me(4)C(6)H(2))RuCl[eta(2)-P,O-PPh(2)(2-O-C(6)H(3)-6-OMe}], 6b, and (eta(6)-1,2,3,4-Me(4)C(6)H(2))RuCl(2)[eta(1)-P-PPh(2){C(6)H(3)(OMe)(2)-2,6}],7b. The phosphine ligand of 6b acted as a bidentate ligand derived from MDMPP: a = 8.074(4) Å, b = 16.816(3) Å, c = 18.916(4) Å, beta = 94.05(3) degrees, monoclinic, P2(1)/n, Z = 4, R = 0.051. Transformation of 7b to 6b readily occurred accompanying an elimination of MeCl. Reaction of 1a with MDMPP eliminated an arene ring to give the octahedral compound RuCl(2)[eta(2)-P,OMe-PPh(2){C(6)H(3)(MeO)(2)-2,6}](2), 8. An X-ray analysis of 8 showed that two MDMPP ligands were in a cis-position: a = 10.596(14) Å, b = 27.586(12) Å, c = 13.036(8) Å, beta = 108.17(7) degrees, monoclinic, P2(1)/n, Z = 4, R = 0.035.

Journal Article↗

An application of electronic asymmetry to highly enantioselective catalytic Diels-Alder reactions.

The compounds (RRu)-[CyRuCl(S)-BINPO]SbF6 and [CyRuCl(S)-TolBINPO]SbF6 (Cy = eta6-cymene), were synthesized from (CyRuCl2)(2) and the appropriate non-C2-symmetric bisphosphine monoxide ligands (S)-BINPO and (S)-TolBINPO (BINPO = 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl) in the presence of NaSbF6. When these complexes were mixed with AgSbF6 the resulting Lewis acids catalyzed the Diels-Alder cycloaddition of cyclopentadiene and methacrolein. The product (2S)-methylbicyclo[2.2.1]hept-5-ene-2-carboxaldehyde was obtained with excellent diastereoselectivity (up to 99%) and enantioselectivity (up to 99%) in several cases. When the complexes containing the analogous C2-symmetric bisphosphine ligands (S)-BINAP and (S)-TolBINAP were employed as catalysts, the Diels-Alder cycloadducts were obtained with much lower enantioselectivity (19 to 50%) for the opposite antipode. Although some of the effect may arise from chelate ring size change, much of the enhanced stereoselectivity of (RRu)-[CyRuCl(S)-BINPO]SbF6 and [CyRuCl(S)-TolBINPO]SbF6 can be attributed to the electronic asymmetry at the stereogenic Ru center.

Catalysis↗

A highly selective arene hydrogenation catalyst that operates in ionic liquid.

The synthesis and structural characterization of [Ru(eta(6)-p-cymene)(eta(2)-TRIPHOS)Cl][PF(6)] is described. The complex is a highly active, homogeneous arene hydrogenation catalyst that is selective toward the hydrogenation of aromatic rings in preference to alkenes, as demonstrated by the hydrogenation of allylbenzene to allylcyclohexane. The catalyst operates in both dichloromethane and ionic liquids and undergoes no decomposition in the latter solvent.

Journal Article↗

Highly selective binding of organometallic ruthenium ethylenediamine complexes to nucleic acids: novel recognition mechanisms.

We have investigated the recognition of nucleic acid derivatives by organometallic ruthenium(II) arene anticancer complexes of the type [(eta(6)-arene)Ru(II)(en)X] where en = ethylenediamine, arene = biphenyl (Bip), tetrahydroanthracene (THA), dihydroanthracene (DHA), p-cymene (Cym) or benzene (Ben), X = Cl(-) or H(2)O using (1)H, (31)P and (15)N ((15)N-en) NMR spectroscopy. For mononucleosides, [(eta(6)-Bip)Ru(en)](2+) binds only to N7 of guanosine, to N7 and N1 of inosine, and to N3 of thymidine. Binding to N3 of cytidine was weak, and almost no binding to adenosine was observed. The reactivity of the various binding sites of nucleobases toward Ru at neutral pH decreased in the order G(N7) > I(N7) > I(N1), T(N3) > C(N3) > A(N7), A(N1). Therefore, pseudo-octahedral diamino Ru(II) arene complexes are much more highly discriminatory between G and A bases than square-planar Pt(II) complexes. Such site-selectivity appears to be controlled by the en NH(2) groups, which H-bond with exocyclic oxygens but are nonbonding and repulsive toward exocyclic amino groups of the nucleobases. For reactions with mononucleotides, the same pattern of site selectivity was observed, but, in addition, significant amounts of the 5'-phosphate-bound species (40-60%) were present at equilibrium for 5'-TMP, 5'-CMP and 5'-AMP. In contrast, no binding to the phosphodiester groups of 3', 5'-cyclic-GMP (cGMP) or cAMP was detected. Reactions with nucleotides proceeded via aquation of [(eta(6)-arene)Ru(en)Cl](+), followed by rapid binding to the 5'-phosphate, and then rearrangement to give N7, N1, or N3-bound products. Small amounts of the dinuclear species, e.g., Ru-O(PO(3))GMPN7-Ru, Ru-O(PO(3))IMPN1-Ru, Ru-O(PO(3))TMPN3-Ru, Ru-N7IMPN1-Ru, and Ru-N7InoN1-Ru were also detected. In competitive binding experiments for [(eta(6)-Bip)Ru(en)Cl](+) with 5'-GMP versus 5'-AMP or 5'-CMP or 5'-TMP, the only final adduct was [(eta(6)-Bip)Ru(en)(N7-GMP)]. Ru-H(2)O species were more reactive than Ru-OH species. The presence of Cl(-) or phosphate in neutral solution significantly decreased the rates of Ru-N7 binding through competitive coordination to Ru. In kinetic studies (pH 7.0, 298 K, 100 mM NaClO(4)), the rates of reaction of cGMP with [(eta(6)-arene)Ru(II)(en)X](n+) (X = Cl(-) or H(2)O) decreased in the order: THA > Bip > DHA >> Cym > Ben, suggesting that N7-binding is promoted by favorable arene-purine hydrophobic interactions in the associative transition state. These findings have revealed that the diamine NH(2) groups, the hydrophobic arene, and the chloride leaving group have important roles in the novel mechanism of recognition of nucleic acids by Ru arene complexes, and will aid the design of more effective anticancer complexes, as well as new site-specific DNA reagents.

Adenosine↗