Impedance technology reveals correlations between cytotoxicity and lipophilicity of mono and bimetallic phosphine complexes.

Label free impedance technology enables the monitoring of cell response patterns post treatment with drugs or other chemicals. Using this technology, a correlation between the lipophilicity of metal complexes and the degree of cytotoxicity was observed. Au(L1)Cl (1), AuPd(L1)(SC4H8)Cl3 (1a) and Au(L2)Cl (2) [L1 = diphenylphosphino-2-pyridine; L2 = 2-(2-(diphenylphosphino)ethyl)-pyridine] were synthesised, in silico drug-likeness and structure-activity relationship monitored using impedance technology. Dose dependent changes in cytotoxicity were observed for the metal complexes resulting in IC50s of 12.5 ± 2.5, 18.3 ± 8.3 and 16.9 ± 0.5 µM for 1, 1a and 2 respectively in an endpoint assay. When a real time impedance assay was used, dose-dependent responses depicting patterns that suggested slower uptake (at a toxic 20 µM) and faster recovery of the cells (at the less toxic 10 µM) of the bimetallic complex (1a) compared to the monometallic complexes (1 and 2) was observed. These data agreed with the ADMET findings of lower aqueous solubility of 1a and non-ideal lipophilicity (AlogP98 of 6.55) over more water soluble 1 and 2 with ideal lipophilicity (4.91 and 5.03 respectively) values. The additional coordination of a Pd atom to the nitrogen atom of a pyridine ring, the sulfur atom of a tetrahydrothiophene moiety and two chlorine atoms in 1a could be contributing to the observed differences when compared to the monometallic complexes. This report presents impedance technology as a means of correlating drug-likeness of lipophilic phosphine complexes containing similar backbone structures and could prove valuable in filtering drug-like compounds in a drug discovery project.

Unique "cradled barbell" complex between a secondary diammonium ion and bis(m-phenylene)-32-crown-10.

[formula: see text] The complexation between N,N'-dibenzyl(m-xylylene)diammonium bis(hexafluorophosphate) (2) and bis(m-phenylene)-32-crown-10 (5) was shown to occur in solution by nuclear magnetic resonance with 1:1 stoichiometry and a Ka value of 189 +/- 19 M-1. A crystal structure of 2:5 revealed a unique 1:1 "exo" or "cradled barbell" complex, instead of the expected pseudorotaxane. This unexpected result illustrates that caution be used in interpreting the results from these types of complexes in the solution and "gas" phases on the basis of crystal structures.

A new cryptand: synthesis and complexation with paraquat.

[formula: see text] Inspired by folded, nonpseudorotaxane complexes of bis(m-phenylene)-32-crown-10 systems, we synthesized a new bicyclic crown ether containing two 1,3,5-phenylene units linked by three tetra(ethyleneoxy) units. The new cryptand forms a "pseudorotaxane-like" inclusion complex with N,N'-dimethyl-4,4'-bipyridinium bis(hexafluorophosphate) with association constant Ka = 6.1 x 10(4) M-1, 100-fold greater than that of an analogous simple crown ether.

Bis(isopropylamino)methylcarbenium tetrakis(pentafluorophenyl)gallate.

The title compound, [MeC(NH(i)Pr)(2)][Ga(C(6)F(5))(4)] crystallizes as discrete ions forming interionic hydrogen bonds of the type N-H.F.

Hydrogen atom and hydride transfer in the reactions of chromium(IV) and chromium(V) complexes with rhodium hydrides. Crystal structure of a superoxorhodium(III) product.

The aquachromyl ion, Cr(IV)aqO2+, reacts with the hydrides L(H2O)RhH2+ (L = L1 = [14]aneN4 and L2 = meso-Me6-[14]aneN4) in aqueous solutions in the presence of molecular oxygen to yield Cr(aq)3+ and the superoxo complexes L(H2O)RhOO2+. At 25 degrees C, the rate constants are approximately 10(4) M(-1) s(-1) (L = L1) and 1.12 x 10(3) M(-1) s(-1) (L = L2). Both reactions exhibit a moderate deuterium isotope effect, kRhH/kRhD = approximately 3 (L1) and 3.3 (L2), but no solvent isotope effect, kH2O/kD2O = 1. The proposed mechanism involves hydrogen atom abstraction followed by the capture of LRh(H2O)2+ with molecular oxygen. There is no evidence for the formation of L(H2O)Rh2+ in the reaction between L(H2O)RhH2+ and (salen)CrVO+. The proposed hydride transfer is supported by the magnitude of the rate constants (L = L1, k = 8,800 M(-1) s(-1); (NH3)4, 2,500; L2, 1,000) and isotope effects (L = L1, kie = 5.4; L2, 6.2). The superoxo complex [L1(CH3CN)RhOO](CF3SO3)2.H2O crystallizes with discrete anions, cations, and solvate water molecules in the lattice. All moieties are linked by a network of hydrogen bonds of nine different types. The complex crystallized in the triclinic space group P1 with a = 9.4257(5) A, b = 13.4119(7) A, c = 13.6140(7) A, alpha = 72.842(1)degrees, beta = 82.082(1) degrees, gamma = 75.414(1) degrees, V = 1587.69(14) A3, and Z = 2.

Macrocyclic hydroperoxocobalt(III) complex: photochemistry, spectroscopy, and crystal structure.

The hydroperoxocobalt complex [L(2)(CH(3)CN)CoOOH](ClO(4))(2).CH(3)CN (L(2) = meso-5,7,7,12,14,14-Me(6)-[14]aneN(4)) crystallizes with discrete anions, cations, and solvate acetonitrile molecules in the lattice. The complex crystallizes in the monoclinic space group P2(1)/n, a = 10.4230(5) A, b = 16.1561(8) A, c = 17.4676(9) A, beta = 92.267(1) degrees, V = 2939.2(3) A(3), Z = 4. The O-O bond length is 1.397(4) A, and the O(2)-O(1)-Co angle spans 117.7 degrees. The O-O stretch in the infrared spectrum appears at 815 cm(-1). The 355- and 266-nm photolysis of acidic aqueous solutions of L(2)(H(2)O)CoOOH(2+) results in homolytic splitting of the Co-O bond and yields L(2)Co(H(2)O)(2)(2+) and HO(2)(*)/O(2)(*-) as the only products. The two fragments were scavenged selectively in separate experiments with O(2) and C(NO(2))(4). There is no evidence for photochemical O-O bond homolysis, presumably because the appropriate optical transition is masked by the HO(2)-to-Co LMCT transition.

Hydrogen bonding in bis(triphenylphosphine-P)iminium hydrogensulfate chloroform solvate.

The title compound, C(36)H(30)NP(2)(+).HSO(4)(-).CHCl(3), consists of discrete ions and well separated chloroform solvate molecules. The central feature of the structure is O-H...O hydrogen bonding between two hydrogensulfate ions related by a crystallographic inversion centre. The chloroform solvate molecule takes part in a well defined C-H...O hydrogen bond.

Hydrolysis, hydrosulfidolysis, and aminolysis of imido(methyl)rhenium complexes.

The tris(imido)methylrhenium complex CH3Re(NAd)3 (1a, Ad = 1-adamantyl) reacts with H2O to give CH3Re(NAd)2O (2a) and AdNH2. The resulting di(imido)oxo species can further react with another molecule of H2O to generate CH3Re(NAd)O2 (3a). The kinetics of these reactions have been studied by means of 1H NMR and UV-vis spectroscopies. The second-order rate constant for the reaction of 1a with H2O at 298 K in C6H6 is 3.3 L mol-1 s-1, which is much larger than the value 1 x 10(-4) L mol-1 s-1 obtained for the reaction between CH3Re(NAr)3 (1b, Ar = 2,6-diisopropylphenyl) and H2O in CH3CN at 313 K. Both 1a and 1b react with H2S to produce the rhenium(VII) sulfide, (CH3Re(NR)2)2(mu-S)2 (4a, R = Ad; 4b, R = Ar), with second-order rate constants of 17 and 1.6 x 10(-4) L mol-1 s-1 in C6H6 and CH3CN, respectively. Complex 4b has been structurally characterized. The crystal data are as follows: space group C2/c, a = 30.4831 (19) A, b = 10.9766 (7) A, c = 18.1645 (11) A, beta = 108.268(1) degrees, V = 5771.5 (6) A3, Z = 4. The reaction between CH3Re(NAr)2O (2b) and H2S also yields the dinuclear compound 4b. Unlike 1b, 1a reacts with aniline derivatives to give mixed imido rhenium complexes.

PhCH=P[MeNCH(2)CH(2)](3)N: a novel ylide for quantitative E selectivity in the Wittig reaction.

PhCH=P[MeNCH(2)CH(2)](3)N (1), a semi-stabilized ylide prepared from the commercially available nonionic base P[MeNCH(2)CH(2)](3)N, reacts with aldehydes to give alkenes in high yield with quantitative E selectivity. In contrast with other ylides, this E selectivity is maintained despite changes in the metal ion of the ionic base used to deprotonate 1, temperature, and solvent polarity. In conjunction with structural parameters gained from the X-ray molecular structure of 1, the pathway to E selectivity in these reactions is rationalized by the Vedejs model of Wittig reaction stereochemistry.

Kinetics and mechanism of the monomerization of a Re(V) dithiolato dimer with monodentate ligands. Electronic and steric effects.

The sulfur-bridged dimeric dithiolato rhenium(V) chelate [CH3(O)Re(eta 2,mu-o-SCH2C6H4S)]2 (D), derived from 2-mercaptothiophenol, was monomerized to give [CH3(O)Re(eta 2-o-SCH2C6H4S)]L (M-L) in benzene upon reaction with various neutral and anionic monodentate ligands (L) such as pyridine and its substituted derivatives, triarylphosphines, dimethyl sulfoxide, 4-picoline-N-oxide, and halide ions. The kinetic observations can readily be interpreted for all ligands by a unified mechanism in which the initial fast formation of a 1:1 (DL) and 1:2 (DL2) adduct is followed by the slow monomerization of each species so formed. The use of different ligands gave insight into different steps of the same multistep mechanism. The kinetics of ligand exchange between free L and the monomeric complexes was also studied; an associative pathway has been proposed to interpret the results. The crystal structures of two new monomeric ML complexes (with L = 4-acetylpyridine and 1,3-diethylthiourea) are reported.

Cationic aluminum alkyl complexes incorporating aminotroponiminate ligands.

The synthesis, structures, and reactivity of cationic aluminum complexes containing the N,N'-diisopropylaminotroponiminate ligand ((i)Pr(2)-ATI(-)) are described. The reaction of ((i)Pr(2)-ATI)AlR(2) (1a-e,g,h; R = H (a), Me (b), Et (c), Pr (d), (i)Bu (e), Cy (g), CH(2)Ph (h)) with [Ph(3)C][B(C(6)F(5))(4)] yields ((i)()Pr(2)-ATI)AlR(+) species whose fate depends on the properties of the R ligand. 1a and 1b react with 0.5 equiv of [Ph(3)C][B(C(6)F(5))(4)] to produce dinuclear monocationic complexes [([(i)Pr(2)-ATI] AlR)(2)(mu-R)][(C(6)F(5))(4)] (2a,b). The cation of 2b contains two ((i)()Pr(2)-ATI)AlMe(+) units linked by an almost linear Al-Me-Al bridge; 2a is presumed to have an analogous structure. 2b does not react further with [Ph(3)C][B(C(6)F(5))(4)]. However, 1a reacts with 1 equiv of [Ph(3)C][B(C(6)F(5))(4)] to afford ((i Pr(2)-ATI)Al(C(6)F(5))(mu-H)(2)B(C(6)F(5))(2) (3) and other products, presumably via C(6)F(5)(-) transfer and ligand redistribution of a [((i)()Pr(2)-ATI)AlH][(C(6)F(5))(4)] intermediate. 1c-e react with 1 equiv of [Ph(3)C][B(C(6)F(5))(4)] to yield stable base-free [((i)Pr(2)-ATI)AlR][B(C(6)F(5))(4)] complexes (4c-e). 4c crystallizes from chlorobenzene as 4c(ClPh).0.5PhCl, which has been characterized by X-ray crystallography. In the solid state the PhCl ligand of 4c(ClPh) is coordinated by a dative PhCl-Al bond and an ATI/Ph pi-stacking interaction. 1g,h react with [Ph(3)C][B(C(6)F(5))(4)] to yield ((i)Pr(2)-ATI)Al(R)(C(6)F(5)) (5g,h) via C(6)F(5)(-) transfer of [((i)Pr(2)-ATI)AlR][(BC(6)F(5))(4)] intermediates. 1c,h react with B(C(6)F(5))(3) to yield ((i)Pr(2)-ATI)Al(R)(C(6)F(5)) (5c,h) via C(6)F(5)(-) transfer of [((i)Pr(2)-ATI)AlR][RB(C(6)F(5))(3)] intermediates. The reaction of 4c-e with MeCN or acetone yields [((i)Pr(2)-ATI)Al(R)(L)][B(C(6)F(5))(4)] adducts (L = MeCN (8c-e), acetone (9c-e)), which undergo associative intermolecular L exchange. 9c-e undergo slow beta-H transfer to afford the dinuclear dicationic alkoxide complex [(((i)Pr(2)-ATI)Al(mu-O(i)()Pr))(2)][B(C(6)F(5))(4)](2) (10) and the corresponding olefin. 4c-e catalyze the head-to-tail dimerization of tert-butyl acetylene by an insertion/sigma-bond metathesis mechanism involving [((i)Pr(2)-ATI)Al(C=C(t)Bu)][B(C(6)F(5))(4)] (13) and [((i)Pr(2)-ATI)Al(CH=C((t)()Bu)C=C(t)Bu)][B(C(6)F(5))(4)] (14) intermediates. 13 crystallizes as the dinuclear dicationic complex [([(i Pr(2)-ATI]Al(mu-C=C(t)Bu))(2)][B(C(6)F(5))(4)](2).5PhCl from chlorobenzene. 4e catalyzes the polymerization of propylene oxide and 2a catalyzes the polymerization of methyl methacrylate. 4c,e react with ethylene-d(4) by beta-H transfer to yield [((i)Pr(2)-ATI)AlCD(2)CD(2)H][B(C(6)F(5))(4)] initially. Polyethylene is also produced in these reactions by an unidentified active species.

Reactions of the protonated dinuclear ruthenium complex [[(eta(5)-C(5)H(3))(2)(SiMe(2))(2)]Ru(2)(CO)(4)(mu-H)]+ with nucleophiles.

Complex [[(eta(5)-C(5)H(3))(2)(SiMe(2))(2)]Ru(2)(CO)(4)(mu-H)](+)BF(4)(-) (1H(+)BF(4)(-)), which features a protonated Ru-Ru bond, reacts with F(-) to give (eta(5)-C(5)H(5))(2)Ru(2)(CO)(4) (2), resulting from the cleavage of both SiMe(2) groups, with I(-) to give the Ru-Ru cleaved product [(eta(5)-C(5)H(3))(2)(SiMe(2))(2)]Ru(2)(CO)(4)(H)(I)(3), and with phosphines (PEt(3), PMe(2)Ph) to give [[(eta(5)-C(5)H(3))(2)(SiMe(2))(2)]Ru(2)(CO)(4)(H)(PR(3))](+) (4a-b). Reaction of 1H(+)BF(4)(-) and NaOMe in THF generates [(eta(5)-C(5)H(4))(2)SiMe(2)]Ru(2)(CO)(4) (5), resulting from the cleavage of a single SiMe(2) group, while the reaction of 1H(+)BF(4)(-) and NaOMe in MeOH generates [mu-eta(5):eta(5)-(C(5)H(3)SiMe(2)OMe)(C(5)H(4))SiMe(2)]Ru(2)(CO)(4) (6), resulting from the partial cleavage of a SiMe(2) group. Reaction of 1H(+)BF(4)(-) and NaSR (R = Me, Et) in THF generates [(eta(5)-C(5)H(3))(2)(SiMe(2))(2)]Ru(2)(CO)(4)(H)(SR) (R = Me, Et; 7a-b), which undergoes rearrangement upon contact with neutral and basic alumina or silica to give complexes [mu-eta(5):eta(1):eta(5)-(C(5)H(3)C=O)(C(5)H(4))(SiMe(2))(2)O]Ru(2)(mu-SR)(CO)(3) (R = Me, Et; 8a-b). Molecular structures of 4a, 6, and 8a as determined by X-ray diffraction studies are also presented.

Syntheses and structures of rhenium(IV) and rhenium(V) complexes with ethanedithiolato ligands.

A novel dimeric rhenium(IV) complex, [Re2(SCH2CH2S)4], and a monomeric methyloxorhenium(V) complex, [CH3ReO(SCH2CH2S)PPh3], were synthesized from methyloxorhenium(V) complexes and characterized crystallographically. The structure of [Re2(SCH2CH2S)4], the formation reaction of which showed surprising demethylation conceivably through the homolytic cleaveage of the rhenium-carbon bond, features distorted trigonal prismatic coordination of sulfurs around the metal center and a rhenium-rhenium triple bond. A revised structure, [Tc2(SCH2CH2S)4], is proposed for a related technetium complex, originally identified as [Tc2(SCH2CH2S)2(SCH=CHS)2] (Tisato et al. Inorg. Chem. 1993, 32, 2042). Additionally, a new compound, CH3Re(O)(SPh)2PPh3, was prepared.

Addition and metathesis reactions of zirconium and hafnium imido complexes.

The zirconium and hafnium imido metalloporphyrin complexes (TTP)M = NArtPr (TTP = meso-5,10,15,20-tetra-p-tolylporphyrinato dianion; M = Zr (1), Hf; AriPr = 2,6-diisopropylphenyl) were used to mediate addition reactions of carbonyl species and metathesis of nitroso compounds. The imido complexes react in a stepwise manner in the presence of 2 equiv of pinacolone to form the enediolate products (TTP)M[OC(tBu)CHC(tBu)(Me)O] (M = Zr (2), Hf (3)), with elimination of H2NAriPr. The bis(mu-oxo) complex [(TTP)ZrO]2 (4) is formed upon reaction of (TTP)Zr = NAriPr with PhNO. Treatment of compound 4 with water or treatment of compound 2 with acetone produced the (mu-oxo)bis(mu-hydroxo)-bridged dimer [(TTP)Zr]2(mu-O)(mu-OH)2 (5). Compounds 2, 4, and 5 were structurally characterized by single-crystal X-ray diffraction.

The lack of C2 molecular symmetry in (1R,2R,3S,6S)-3,6-dibenzyloxycyclohex-4-ene-1,2-diol.

The results of a single-crystal X-ray experiment and density functional theory calculations performed for the title compound, C20H22O4, demonstrate that the lowest energy conformation of this molecule does not contain C2 molecular symmetry.

Reactions of halofluorocarbons with group 6 complexes M(C(5)H(5))(2)L (M = Mo, W; L = C(2)H(4), CO). Fluoroalkylation at molybdenum and tungsten, and at cyclopentadienyl or ethylene ligands.

The molybdenum(II) and tungsten(II) complexes [MCp(2)L] (Cp = eta(5)-cyclopentadienyl; L = C(2)H(4), CO) react with perfluoroalkyl iodides to give a variety of products. The Mo(II) complex [MoCp(2)(C(2)H(4))] reacts with perfluoro-n-butyl iodide or perfluorobenzyl iodide with loss of ethylene to give the first examples of fluoroalkyl complexes of Mo(IV), MoCp(2)(CF(2)CF(2)CF(2)CF(3))I (8) and MoCp(2)(CF(2)C(6)F(5))I (9), one of which (8) has been crystallographically characterized. In contrast, the CO analogue [MoCp(2)(CO)] reacts with perfluorobenzyl iodide without loss of CO to give the crystallographically characterized salt, [MoCp(2)(CF(2)C(6)F(5))(CO)](+)I(-) (10), and the W(II) ethylene precursor [WCp(2)(C(2)H(4))] reacts with perfluorobenzyl iodide without loss of ethylene to afford the salt [WCp(2)(CF(2)C(6)F(5))(C(2)H(4))](+)I(-) (11). These observations demonstrate that the metal-carbon bond is formed first. In further contrast the tungsten precursor [WCp(2)(C(2)H(4))] reacts with perfluoro-n-butyl iodide, perfluoro-iso-propyl iodide, and pentafluorophenyl iodide to give fluoroalkyl- and fluorophenyl-substituted cyclopentadienyl complexes WCp(eta(5)-C(5)H(4)R(F))(H)I (12, R(F) = CF(2)CF(2)CF(2)CF(3); 15, R(F) = CF(CF(3))(2); 16, R(F) = C(6)F(5)); the Mo analogue MoCp(eta(5)-C(5)H(4)R(F))(H)I (14, R(F) = CF(CF(3))(2)) is obtained in similar fashion. The tungsten(IV) hydrido compounds react with iodoform to afford the corresponding diiodides WCp(eta(5)-C(5)H(4)R(F))I(2) (13, R(F) = CF(2)CF(2)CF(2)CF(3); 18, R(F) = CF(CF(3))(2); 19, R(F) = C(6)F(5)), two of which (13 and 19) have been crystallographically characterized. The carbonyl precursors [MCp(2)(CO)] each react with perfluoro-iso-propyl iodide without loss of CO, to afford the exo-fluoroalkylated cyclopentadiene M(II) complexes MCp(eta(4)-C(5)H(5)R(F))(CO)I (21, M = Mo; 22, M = W); the exo-stereochemistry for the fluoroalkyl group is confirmed by an X-ray structural study of 22. The ethylene analogues [MCp(2)(C(2)H(4))] react with perfluoro-tert-butyl iodide to yield the products MCp(2)[(CH(2)CH(2)C(CF(3))(3)]I (25, M = Mo; 26, M = W) resulting from fluoroalkylation at the ethylene ligand. Attempts to provide positive evidence for fluoroalkyl radicals as intermediates in reactions of primary and benzylic substrates were unsuccessful, but trapping experiments with CH(3)OD (to give R(F)D, not R(F)H) indicate that fluoroalkyl anions are the intermediates responsible for ring and ethylene fluoroalkylation in the reactions of secondary and tertiary fluoroalkyl substrates.

Atom transfer reactions of (TTP)Ti(eta 2-3-hexyne): synthesis and molecular structure of trans-(TTP)Ti[OP(Oct)3]2.

Atom and group transfer reactions were found to occur between heterocumulenes and (TTP)Ti(eta 2-3-hexyne), 1 (TTP = meso-5,10,15,20-tetra-p-tolylporphyrinato dianion). The imido derivatives (TTP)Ti=NR (R = iPr, 2; tBu, 3) were produced upon treatment of complex 1 with iPrN=C=NiPr, iPrNCO, or tBuNCO. Reactions between complex 1 and CS2, tBuNCS, or tBuNCSe afforded the chalcogenido complexes, (TTP)Ti=Ch (Ch = Se, 4; S, 5). Treatment of complex 1 with 2 equiv of PEt3 yielded the bis(phosphine) complex, (TTP)Ti(PEt3)2, 6. Although (TTP)Ti(eta 2-3-hexyne) readily abstracts oxygen from epoxides and sulfoxides, the reaction between 1 and O=P(Oct)3 did not result in oxygen atom transfer. Instead, the paramagnetic titanium(II) derivative (TTP)Ti[O=P(Oct)3]2, 7, was formed. The molecular structure of complex 7 was determined by single-crystal X-ray diffraction: Ti-O distance 2.080(2) A and Ti-O-P angle of 138.43(10) degrees. Estimates of Ti=O, Ti=S, Ti=Se, and Ti=NR bond strengths are discussed.

Chemistry of coordinated nitroxyl. Reagent-specific protonations of trans-Re(CO)(2)(NO)(PR(3))(2) (R = Ph, Cy) that give the neutral nitroxyl complexes cis,trans-ReCl(CO)(2)(NH=O)(PR(3))(2) or the cationic hydride complex [trans,trans-ReH(CO)(2)(NO)(PPh(3))(2)(+)][SO(3)CF(3)(-)].

The reactions of hydrochloric and triflic acids with the five-coordinate nitrosyl complexes trans-Re(CO)(2)(NO)(PR(3))(2) (2a, R = Ph; 2b, R = Cy) have been investigated. Reaction of anhydrous HCl with 2 results in a formal protonation of the nitrosyl ligand and addition of chloride to the metal, giving the neutral nitroxyl complex cis,trans-ReCl(CO)(2)(NH=O)(PR(3))(2) (3a, R = Ph; 3b, R = Cy). Reaction of Brønsted bases with 3a or 3b results in clean conversion of 3 to 2 when the base is appropriately strong (pK(b) approximately 7). Addition of HOSO(2)CF(3) to solutions of 2a results in protonation at the metal and formation of the cationic rhenium hydride [trans,trans-ReH(CO)(2)(NO)(PPh(3))(2)(+)][SO(3)CF(3)(-)] (4) in 74% yield; the deuteride [trans,trans-Re((2)H)(CO)(2)(NO)(PPh(3))(2)(+)][SO(3)CF(3)(-)] (4-d) was analogously prepared from (2)HOSO(2)CF(3). 4 crystallized from CH(2)Cl(2)/Et(2)O solution in the orthorhombic space group Pnma, with a = 17.2201(2) A, b = 23.6119(3) A, c = 9.2380(2) A, and Z = 4. The least-squares refinement converged to R(F) = 0.039 and R(wF(2)()) = 0.063 for the 4330 unique data with I > 2 sigma(I). The structure of 4 shows that the hydride (Re-H = 1.74 A) occupies the position trans to the linear nitrosyl ligand (Re-N-O = 178.1(4) degrees ) in the pseudooctahedral complex cation. Complex 4 does not react with chloride to give 3a. DFT calculations carried out on free nitroxyl and its model complexes [Re(CO)(5)(NH=O)(+)] (5), [mer,trans-Re(CO)(3)(NH=O)(PH(3))(2)(+)] (6), and cis,trans-ReCl(CO)(2)(NH=O)(PH(3))(2) (7) indicate that coordinated nitroxyl acts as both a sigma-donor and pi-acceptor ligand, consistent with the observed trend for nu(NO) in free HN=O (1563 cm(-1)), [mer,trans-Re(CO)(3)(NH=O)(PPh(3))(2)(+)] (1, 1391 cm(-1)), 3a (1376 cm(-1)), and 3b (1335 cm(-1)).

Amine-chelated aryllithium reagents--structure and dynamics.

Multinuclear NMR studies of five-membered-ring amine chelated aryllithium reagents 2-lithio-N,N-dimethylbenzylamine (1), the diethylamine and diisopropylamino analogues (2, 3), and the o-methoxy analogue (4), isotopically enriched in (6)Li and (15)N, have provided a detailed picture of the solution structures in ethereal solvents (usually in mixtures of THF and dimethyl ether, ether, and 2,5-dimethyltetrahydrofuran). The effect of cosolvents such as TMEDA, PMDTA, and HMPA has also been determined. All compounds are strongly chelated, and the chelation is not disrupted by these cosolvents. Reagents 1, 2, and 3 are dimeric in solvents containing a large fraction of THF. Below -120 degrees C, three chelation isomers of the dimers are detectable by NMR spectroscopy: one (A) with both nitrogens coordinated to one lithium of the dimer, and two (B and C) in which each lithium bears one chelating group. Dynamic NMR studies have provided rates and activation energies for the interconversion of the 1-A, 1-B, and 1-C isomers. They interconvert either by simple ring rotation, which interconverts B and C, or by amine decoordination (probably associative, DeltaG(++)(-93) = 8.5 kcal/mol), which can interconvert all of the isomers. The dimers of 1 are thermodynamically more stable than those of model systems such as phenyllithium, o-tolyllithium, or 2-isoamylphenyllithium (5, DeltaDeltaG > or = 3.3 kcal/mol). They are not detectably deaggregated by TMEDA or PMDTA, although HMPA causes partial deaggregation. The dimers are also more robust kinetically with rates of interaggregate exchange, measured by DNMR line shape analysis of the C-Li signal, orders of magnitude smaller than those of models (DeltaDeltaG(++) > or = 4.4 kcal/mol). Similarly, the mixed dimer of 1 and phenyllithium, 13, is kinetically more stable than the phenyllithium dimer by >2.2 kcal/mol. X-ray crystal structures of the TMEDA solvate of 1-A and the THF solvate of 3-B showed them to be dimeric and chelated in the solid state as well. Compound 4, which has a methoxy group ortho to the C-Li group, differs from the others in being only partially dimeric in THF, presumably for steric reasons. This compound is fully deaggregated by 1 equiv of HMPA. Excess HMPA leads to the formation of ca. 15% of a triple ion (4-T) in which both nitrogens appear to be chelated to the central lithium.

(F(8)TPP)Fe(II)/O(2) reactivity studies [F(8)TPP = tetrakis(2,6-difluorophenyl)porphyrinate(2-)]: spectroscopic (UV-Visible and NMR) and kinetic study of solvent-dependent (Fe/O(2) = 1:1 or 2:1) reversible O(2)-reduction and ferryl formation.

In this report, we describe in detail the O(2)-binding chemistry of the metalloporphyrin (F(8)TPP)Fe(II) (1). This complex was synthesized from aqueous dithionite reduction of (F(8)TPP)Fe(III)-Cl (X-ray structure reported: C(55)H(36)ClF(8)FeN(4)O; a = 13.6517(2) A, b = 13.6475(2) A, c = 26.3896(4), alpha = 90 degrees, beta = 89.9776(4) degrees, gamma = 90 degrees; monoclinic, P2(1)/c, Z = 4). Complex 1 crystallizes from toluene/heptane solvent system as a bis(toluene) solvate, (F(8)TPP)Fe(II).(C(7)H(8))(2), with ferrous ion in the porphyrin plane (C(58)H(36)F(8)FeN(4); a = 20.9177(2) A, b = 11.7738(2) A, c = 19.3875(2), alpha = 90 degrees, beta = 108.6999(6) degrees, gamma = 90 degrees; monoclinic, C2/c, Z = 4; Fe-N(4)(av) = 2.002 A; N-Fe-N (all) = 90.0 degrees ). Close metal-arene contacts are also observed at 3.11-3.15 A. Upon oxygenation of 1 at 193 K in coordinating solvents, UV-visible and (2)H and (19)F NMR spectroscopies revealed the presence of a reversibly formed dioxygen adduct, formulated as the heme-superoxo complex (S)(F(8)TPP)Fe(III)-(O(2)(-)) (2) (S = solvent) [(i) tetrahydrofuran (THF) solvent: UV-visible, 416 (Soret), 536 nm; (2)H NMR: delta(pyrrole) 8.9 ppm; (ii) EtCN solvent: UV-visible, 414 (Soret), 536 nm; (iii) acetone solvent: UV-visible, 416 (Soret), 537 nm; (2)H NMR: delta(pyrrole) 8.9 ppm]. Dioxygen-uptake manometry (THF, 193 K) revealed an O(2):1 oxygenation stoichiometry of 1.02:1, consistent with the heme-superoxo formulation of 2. Stopped-flow UV-visible spectrophotometry studies of the (F(8)TPP)Fe(II) (1)/O(2) reaction in EtCN and THF solvents were able to provide kinetic and thermodynamic insight into the reversible formation of 2 [(i) EtCN: Delta H degrees = -40 +/- 5 kJ/mol; Delta S degrees = -105 +/- 23 J/(K mol); k(1) = (5.57 +/- 0.04) x 10(3) M(-)(1) s(-)(1) (183 K); Delta H(++) = 38.6 +/- 0.2 kJ/mol; Delta S(++) = 42 +/- 1 J/(K mol); (ii) THF: Delta H* = -37.5 +/- 0.4 kJ/mol; Delta S* = -109 +/- 2 J/(K mol)]. The (F(8)TPP)Fe(II) (1)/O(2) reaction was also examined at reduced temperatures in noncoordinating solvents (toluene, CH(2)Cl(2)), where UV-visible and (2)H and (19)F NMR spectroscopies also revealed the presence of a reversibly formed adduct, formulated as the peroxo-bridged dinuclear complex [(F(8)TPP)Fe(III)](2)-(O(2)(2)(-)) (3) [CH(2)Cl(2): UV-visible, 414 (Soret), 535 nm; (2)H NMR, delta(pyrrole) 17.5 ppm]. Dioxygen-uptake spectrophotometric titrations revealed a stoichiometry of 2 (F(8)TPP)Fe(II) (1) per O(2) upon full formation of 3. Addition of a nitrogenous base, 4-(dimethylamino)pyridine, to a cold solution of 3 in dichloromethane gave rapid formation of the iron(IV)-oxo ferryl species (DMAP)(F(8)TPP)Fe(IV)==O (4), based upon UV-visible [417 (Soret), 541 nm] and (2)H NMR (delta(pyrrole) = 3.5 ppm) spectroscopic characterization. These detailed investigations into the O(2)-adducts and "ferryl" species formed from (F(8)TPP)Fe(II) (1) may be potentially important for a full understanding of our ongoing heme-copper oxidase model studies, which employ 1 or similar "tethered" (i.e., covalently attached Cu-chelate) porphyrin analogues in heme/Cu heterobinuclear systems.