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1.
Angew Chem Int Ed Engl ; 57(3): 749-754, 2018 01 15.
Artigo em Inglês | MEDLINE | ID: mdl-29152832

RESUMO

An extended π-system containing two [3]cumulene fragments separated by a p-carboquinoid and stabilized by two capping N-heterocyclic carbenes (NHCs) has been prepared. Mono- and bis(imidazolidinium ethynyl) cations have also been synthesized from the reaction of an NHC with phenylethynyl bromide or 1,4-bis(bromoethynyl)benzene. Cyclic voltammetry coupled with synthetic and structural studies showed that the dication is readily reduced to a neutral, singlet bis-1,4-([3]cumulene)-p-carboquinoid as a result of the π-accepting properties of the capping NHCs.

2.
Angew Chem Int Ed Engl ; 57(6): 1707-1711, 2018 02 05.
Artigo em Inglês | MEDLINE | ID: mdl-29272562

RESUMO

An improved synthetic pathway to the nanobelt-like 1,1,9,9-tetramethyl[9](2,11)teropyrenophane has been developed, and enables the synthesis of gram quantities of material. Key innovations are the development of a sequential chlorination/Friedel-Crafts alkylation reaction, a sequential iodination/Wurtz coupling reaction, and a room-temperature teropyrene-forming reaction. The teropyrenophane was found to form a very stable radical cation and undergo a completely regioselective fourfold bromination reaction.

3.
Chemistry ; 23(6): 1278-1290, 2017 Jan 26.
Artigo em Inglês | MEDLINE | ID: mdl-27783442

RESUMO

The first lanthanide complexes with a redox-active sulfur diimide ligand, [LnCp*2 (Me3 SiN=)2 S] (Ln=Sm, Eu, Yb; Cp*=η5 -C5 Me5 ), are reported. The complexes were synthesized by using [LnCp*2 (THF)2 ] and (Me3 SiN=)2 S and have been thoroughly characterized by single-crystal X-ray diffraction, EPR spectroscopy, UV/Vis/NIR electronic absorption spectroscopy and SQUID magnetometry. The results, as interpreted by CASSCF/SOC-RASSI calculations providing a non-perturbative treatment of spin-orbit coupling, indicate that these paramagnetic complexes are best described as Ln3+ and [(Me3 SiN=)2 S]-. adducts. As such, these complexes contain the first isolated and structurally characterized acyclic [(RN=)2 S]-. radical anions.

4.
Dalton Trans ; 44(41): 18247-59, 2015 Nov 07.
Artigo em Inglês | MEDLINE | ID: mdl-26426745

RESUMO

The reactions of dipyridylmethane (dpma) with group 13 trichlorides were investigated in 1 : 1 and 1 : 2 molar ratios using NMR spectroscopy and X-ray crystallography. With 1 : 1 stoichiometry and Et2O as solvent, reactions employing AlCl3 or GaCl3 gave mixtures of products with the salt [(dpma)2MCl2](+)[MCl4](-) (M = Al, Ga) as the main species. The corresponding reactions in 1 : 2 molar ratio gave similar mixtures but with [(dpma)MCl2](+)[MCl4](-) as the primary product. Pure salts [(dpma)AlCl2](+)[Cl](-) and [(dpma)AlCl2](+)[AlCl4](-) could be obtained by performing the reactions in CH3CN. In the case of InCl3, a neutral monoadduct (dpma)InCl3 formed regardless of the stoichiometry employed. A neutral adduct (dpma)(BCl3)2 was obtained from the reaction between dpma and BCl3 in Et2O using 1 : 2 stoichiometry. With 1 : 1 molar ratio of reagents, a mixture of products and deprotonation of the methylene bridge in [(dpma)BCl2](+) was observed. The experimental data showed that the structural flexibility of the dpma ligand results in more diverse coordination chemistry with group 13 elements than that observed for bipyridine (bpy), while computational investigations indicated that the investigated metal-ligand interactions are, to a first approximation, independent of the ligand type. Electrochemical and chemical attempts to reduce the cations [(dpma)MCl2](+) showed that, in stark contrast to the chemistry of the related [(bpy)BCl2](+) cation, the neutral radicals [(dpma)MCl2]˙ are extremely unstable. Differences in the redox behaviour of dpma and bpy could be rationalized with the electronic structure of the ligand and that of the methylene bridge in particular. As a whole, the facile reactivity of the methylene bridge in the dpma ligand renders it amenable to further reactivity and functionalization that is not possible in the case of bpy.

5.
Chemistry ; 20(15): 4447-59, 2014 Apr 07.
Artigo em Inglês | MEDLINE | ID: mdl-24595990

RESUMO

The perhalogenated closo-dodecaborate dianions [B12 X12 ](2-) (X=H, F, Cl, Br, I) are three-dimensional counterparts to the two-dimensional aromatics C6 X6 (X=H, F, Cl, Br, I). Whereas oxidation of the parent compounds [B12 H12 ](2-) and benzene does not lead to isolable radicals, the perhalogenated analogues can be oxidized by chemical or electrochemical methods to give stable radicals. The chemical oxidation of the closo-dodecaborate dianions [B12 X12 ](2-) with the strong oxidizer AsF5 in liquid sulfur dioxide (lSO2 ) yielded the corresponding radical anions [B12 X12 ](⋅-) (X=F, Cl, Br). The presence of radical ions was proven by EPR and UV/Vis spectroscopy and supported by quantum chemical calculations. Use of an excess amount of the oxidizing agent allowed the synthesis of the neutral perhalogenated hypercloso-boranes B12 X12 (X=Cl, Br). These compounds were characterized by single-crystal X-ray diffraction of dark blue B12 Cl12 and [Na(SO2 )6 ][B12 Br12 ]⋅B12 Br12 . Sublimation of the crude reaction products that contained B12 X12 (X=Cl, Br) resulted in pure dark blue B12 Cl12 or decomposition to red B9 Br9 , respectively. The energetics of the oxidation processes in the gas phase were calculated by DFT methods at the PBE0/def2-TZVPP level of theory. They revealed the trend of increasing ionization potentials of the [B12 X12 ](2-) dianions by going from fluorine to bromine as halogen substituent. The oxidation of all [B12 X12 ](2-) dianions was also studied in the gas phase by mass spectrometry in an ion trap. The electrochemical oxidation of the closo-dodecaborate dianions [B12 X12 ](2-) (X=F, Cl, Br, I) by cyclic and Osteryoung square-wave voltammetry in liquid sulfur dioxide or acetonitrile showed very good agreement with quantum chemical calculations in the gas phase. For [B12 X12 ](2-) (X=F, Cl, Br) the first and second oxidation processes are detected. Whereas the first process is quasi-reversible (with oxidation potentials in the range between +1.68 and +2.29 V (lSO2 , versus ferrocene/ferrocenium (Fc(0/+) ))), the second process is irreversible (with oxidation potentials ranging from +2.63 to +2.71 V (lSO2 , versus Fc(0/+) )). [B12 I12 ](2-) showed a complex oxidation behavior in cyclic voltammetry experiments, presumably owing to decomposition of the cluster anion under release of iodide, which also explains the failure to isolate the respective radical by chemical oxidation.

6.
Molecules ; 19(2): 1956-75, 2014 Feb 12.
Artigo em Inglês | MEDLINE | ID: mdl-24526253

RESUMO

The title salt, triphenyl(P,P,P-triphenylphosphineimidato-kN)-phosphorus(1+) 1,3,5,7-tetrathia(1,5-SIV)-2,4,6,8,9-pentaazabicyclo[3.3.1]nona-1,4,6,7-tetraene(1-), CAS [48236-06-2], prepared by the literature method, is found by crystallography to be a 1:1 CH3CN solvate. Disorder exists for the N atoms of the anion. A VT crystal structure study was conducted at 100 K, 120 K, 140 K, 172 K, 200 K, 240 K and 280 K. The 100 K structure is superior, with only 10% of a second anion position oppositely-oriented w.r.t the diad axis of point group 2mm. At 120 K, an adjacent two-site disorder is encountered, but at higher temperatures three-site disorder with both opposite and adjacent placements of S4N5- ions is required w.r.t. the primary component. At 240 and especially 280 K, the anion nitrogen atoms appear fully scrambled amongst the six possible sites on the edges of an S4 tetrahedron with 83.3% occupancy for each. The PPN+ geometry does not show strong cation-cation interactions. However, there are numerous supramolecular contacts corresponding mostly to non-classical H-bonds between PPN+ ions and S4N5- as well as CH3CN. The geometry of the anion is corroborated from B3LYP/6-311++G(3df) DFT calculations, and the infra-red spectrum was assigned with excellent agreement between experimental and calculated frequencies.


Assuntos
Ânions/química , Modelos Moleculares , Estrutura Molecular , Sais/química , Íons , Teoria Quântica , Temperatura , Difração de Raios X
7.
Chemphyschem ; 14(14): 3199-203, 2013 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-23943606

RESUMO

Chalcogen dications: Facile synthesis of E--E bonded dications can be readily achieved. Radical cations are identified as the intermediates.

8.
J Am Chem Soc ; 135(30): 11205-15, 2013 Jul 31.
Artigo em Inglês | MEDLINE | ID: mdl-23808375

RESUMO

Activation barriers to the electrochemical oxidation for the series PPh3-n(dipp)n (dipp = 2,6-diisopropylphenyl) in CH2Cl2/Bu4NPF6 were measured using large amplitude FT ac voltammetry. Increasing substitution across this series, which offers the widest range of steric requirements across any analogous series of triarylphosphines reported to date, increases the energetic barrier to electron transfer; values of 18, 24, and 25 kJ mol(-1) were found for compounds with n = 1, 2, and 3, respectively. These values are significantly greater than those calculated for outer sphere activation barriers, with deviations between observed and calculated values increasing with the number of dipp ligands. This suggests that the steric congestion afforded by these bulky substituents imposes significant reorganizational energy on the electron transfer processes. This is the first investigation of the effect of sterics on the kinetics of heterogeneous electron transfer across a structurally homologous series. Increased alkyl substitution across the series also increases the chemical reversibility of the oxidations and decreases the oxidation peak potentials. As the compounds for which n = 1 and 2 are novel, the synthetic strategies employed in their preparation are described, along with their full spectroscopic, physical, and crystallographic characterization. Optimal synthesis when n = 1 is via a Grignard reagent, whereas when n = 2 an aryl copper reagent must be employed, as use of a Grignard results in reductive coupling. Chemical oxidation studies were performed to augment the electrochemical work; the O, S, and Se oxidation products for the parent triarylphosphines for which n = 1 and 2 were isolated and characterized.

9.
Chemistry ; 19(5): 1784-95, 2013 Jan 28.
Artigo em Inglês | MEDLINE | ID: mdl-23233412

RESUMO

The range of electrochemical stability of a series of weakly coordinating halogenated (Hal=F, Cl, Br, I) 1-carba-closo-dodecaborate anions, [1-R-CB(11)X(5)Y(6)](-) (R=H, Me; X=H, Hal, Me; Y=Hal), has been established by using quantum chemical calculations and electrochemical methods. The structures of the neutral and dianionic radicals, as well as the anions, have been optimized by using DFT calculations at the PBE0/def2-TZVPP level. The calculated structures are in good agreement with existing experimental data and with previous calculations. Their gas-phase ionization energies and electron affinities were calculated based on their optimized structures and were compared with experimental (cyclic and square-wave) voltammetry data. Electrochemical oxidation was performed in MeCN at room temperature and in liquid sulfur dioxide at lower temperatures. All of the anions show a very high resistance to the onset of oxidation (2.15-2.85 V versus Fc(0/+)), with only a minor dependence of the oxidation potential on the different halogen substituents. In contrast, the reduction potentials in MeCN are strongly substituent dependent (-1.93 to -3.32 V versus Fc(0/+)). The calculated ionization energies and electron affinities correlate well with the experimental redox potentials, which provide important verification of the thermodynamic validity of the mostly irreversible redox processes that are observed for this series. The large electrochemical windows that are afforded by these anions indicate their suitability for electrochemical applications, for example, as supporting electrolytes.

10.
Inorg Chem ; 51(21): 11837-50, 2012 Nov 05.
Artigo em Inglês | MEDLINE | ID: mdl-23098074

RESUMO

A new, easily synthesized diphosphine based on a heterocyclic 1,3,2-diazaphospholidine framework has been prepared. Due to the large, sterically encumbering Dipp groups (Dipp = 2,6-diisopropylphenyl) on the heterocyclic ring, the diphosphine undergoes homolytic cleavage of the P-P bond in solution to form two phosphinyl radicals. The diphosphine has been reacted with O(2), S(8), Se, Te, and P(4), giving products that involve insertion of elements between the P-P bond to yield the related phosphinic acid anhydride, sulfide/disulfide, selenide, telluride, and a butterfly-type perphospha-bicyclobutadiene structure with a trans,trans-geometry. All molecules have been characterized by multinuclear NMR spectroscopy, elemental analysis, and single-crystal X-ray crystallography. Variable-temperature EPR spectroscopy was utilized to study the nature of the phosphinyl radical in solution. Electronic structure calculations were performed on a number of systems from the parent diphosphine [H(2)P](2) to amino-substituted [(H(2)N)(2)P](2) and cyclic amino-substituted [(H(2)C)(2)(NH)(2)P](2); then, bulky substituents (Ph or Dipp) were attached to the cyclic amino systems. Calculations on the isolated diphosphine at the B3LYP/6-31+G* level show that the homolytic cleavage of the P-P bond to form two phosphinyl radicals is favored over the diphosphine by ~11 kJ/mol. Furthermore, there is a significant amount of relaxation energy stored in the ligands (52.3 kJ/mol), providing a major driving force behind the homolytic cleavage of the central P-P bond.

11.
Acta Crystallogr Sect E Struct Rep Online ; 67(Pt 12): o3137, 2011 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-22199665

RESUMO

The title compound, C(10)H(10)Cl(3)N(3), features a delocalized unsaturated N C N C N chain and strong intra-molecular N-H⋯N hydrogen bonding across the chelate ring and also intra-molecular N-H⋯Cl contacts to a CCl(3)-group Cl atom. The only inter-molecular contacts in the lattice are non-classical hydrogen bonds between methyl and CCl(3) groups. The pseudo-six-membered ring is distinctly non-planar by virtue of rotation about the N-C bond between the carboximidamide and imine components [C-N-C-N torsion angle = -23.6 (2) °].

12.
Acta Crystallogr C ; 67(Pt 8): o273-7, 2011 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-21817791

RESUMO

In the solid state, 4-methoxy-N'-(2,2,2-trichloroethanimidoyl)benzene-1-carboximidamide, C(10)H(10)Cl(3)N(3)O, (I), N'-(2,2,2-trichloroethanimidoyl)benzene-1-carboximidamide, C(9)H(8)Cl(3)N(3), (II), 4-chloro-N'-(2,2,2-trichloroethanimidoyl)benzene-1-carboximidamide, C(9)H(7)Cl(4)N(3), (III), 4-bromo-N'-(2,2,2-trichloroethanimidoyl)benzene-1-carboximidamide, C(9)H(7)BrCl(3)N(3), (IV), and 4-trifluoromethyl-N'-(2,2,2-trichloroethanimidoyl)benzene-1-carboximidamide, C(10)H(7)Cl(3)F(3)N(3), (V), display strong intramolecular N-H...N hydrogen bonding across the chelate ring and also intramolecular N-H...Cl contacts. Additional intermolecular hydrogen bonds link the molecules into chains, double chains or sheets in all cases except for compound (V). For compound (II), there are three independent molecules per asymmetric unit.

13.
Inorg Chem ; 50(11): 5123-36, 2011 Jun 06.
Artigo em Inglês | MEDLINE | ID: mdl-21539355

RESUMO

A general synthetic route to 3-trifluoromethyl-5-aryl-1λ(3)-1,2,4,6-thiatriazinyl radicals was developed. X-ray structures were obtained for all five neutral radicals and show that they exist in the solid state as cofacial dimers linked by S···S contacts. X-ray structures were also obtained for two of the precursor chlorothiatriazines along with several aryl N-imidoylamidines, p-methoxybenzamidine, and N-chlorosulfonyl-N,N'-benzamidine. Cyclic voltammetric studies were performed on the [R(2)C(2)N(3)S](•) radicals in CH(3)CN and CH(2)Cl(2) with [(n)Bu(4)N][PF(6)] as the supporting electrolyte under vacuum conditions in an all-glass electrochemical cell. The results provide quasi-reversible formal potentials for the [R(2)C(2)N(3)S](-/0) process in the range of -0.61 to -0.47 V, irreversible peak potentials for the [R(2)C(2)N(3)S](0/+) process from 0.59 to 0.91 V at lower concentrations, and the appearance of a second, reversible oxidation process from 0.69 to 0.94 V at higher concentrations (versus the Fc(0/+) couple; Fc = ferrocene). This behavior was indicative of monomer-dimer equilibrium in solution, as ascertained from digital models of the voltammograms. There is a small but measurable trend in both the oxidation and reduction potentials with varying remote aryl substituents. EPR spectra were obtained for all five neutral radicals in CH(2)Cl(2) solutions, which confirm the concentration of the unpaired electron density on the heterocyclic core. Trends were also seen in the hyperfine splitting constants a(N) with varying remote aryl substituents. Calculations were performed for all three oxidation states of the [R(2)C(2)N(3)S](-/•/+) monomeric rings; the resulting theoretical redox energies correlate well with solution phase voltammetric data.

15.
Inorg Chem ; 48(19): 9454-62, 2009 Oct 05.
Artigo em Inglês | MEDLINE | ID: mdl-19715306

RESUMO

Voltammetric studies of S(2)N(2) employing both cyclic voltammetry (CV) and rotating disk electrode (RDE) methods on GC electrodes at room temperature (RT) revealed two irreversible reduction processes at about -1.4 V and -2.2 V in CH(3)CN, CH(2)Cl(2), and tetrahydrofuran (vs ferrocene) and no observable oxidation processes up to the solvent limit when the scan is initially anodic. However, after cycling the potential through -1.4 V, two new couples appear near -0.3 V and -1.0 V due to [S(3)N(3)](-/0) and [S(4)N(4)](-/0) respectively. The diffusion coefficient D for S(2)N(2) was determined to be 9.13 x 10(-6) cm(2) s(-1) in CH(2)Cl(2) and 7.65 x 10(-6) cm(2) s(-1) in CH(3)CN. Digital modeling of CVs fits well to a mechanism in which [S(2)N(2)](-*) couples rapidly with S(2)N(2) to form [S(4)N(4)](-*), which then decomposes to [S(3)N(3)](-). In situ electron paramagnetic resonance (EPR) spectroelectrochemical studies of S(2)N(2) in both CH(2)Cl(2) and CH(3)CN resulted in the detection of strong EPR signals from [S(4)N(4)](-*) when electrolysis is conducted at -1.4 V; at more negative voltages, spectra from transient adsorbed radicals are observed. In moist solvent or with added HBF(4), a longer-lived spectrum is obtained due to the neutral radical [S(2)N(2)H](*), identified by simulation of the EPR spectrum and density functional theory (DFT) calculations. The chemical reduction of S(2)N(2) with Na[C(10)H(8)] or Na[Ph(2)CO] produces [Na(15-crown-5)][S(3)N(3)], while reduction with cobaltocene gives [Cp(2)Co][S(3)N(3)]. The X-ray structure of the former reveals a strong interaction (Na...N = 2.388(5) A) between the crown ether-encapsulated Na(+) cation and one of the nitrogen atoms of the essentially planar six-membered cyclic anion [S(3)N(3)](-).

16.
Inorg Chem ; 48(15): 7294-306, 2009 Aug 03.
Artigo em Inglês | MEDLINE | ID: mdl-19588981

RESUMO

Voltammetric studies of S(4)N(4) employing both cyclic (CV) and rotating disk (RDE) methods in CH(2)Cl(2) at a glassy carbon electrode reveal a one-electron reduction at -1.00 V (versus ferrocene/ferrocenium), which produces a second redox couple at -0.33 V, confirmed to be the electrochemically generated [S(3)N(3)](-) by CV studies on its salts. Diffusion coefficients (CH(2)Cl(2)/0.4 M [(n)Bu(4)N][PF(6)]) estimated by RDE methods: S(4)N(4), 1.17 x 10(-5) cm(2) s(-1); [S(3)N(3)](-), 4.00 x 10(-6) cm(2) s(-1). Digital simulations of the CVs detected slow rates of electron transfer for both couples and allowed for a determination of rate constants for homogeneous chemical reaction steps subsequent to electron transfer. The common parameters (k(f1) = 2.0 +/- 0.5 s(-1), k(s1) = 0.034 +/- 0.004 cm s(-1) for [S(4)N(4)](-/0); k(f2) = 0.4 +/- 0.2 s(-1), k(s2) = 0.022 +/- 0.005 cm s(-1) for [S(3)N(3)](-/0) at T = 21 +/- 2 degrees C) fit well to a "square-scheme" mechanism over the entire range of data with first order decay of both redox products. An alternate model could also be fit wherein [NS](*) liberated in the first step reacts with formed [S(3)N(3)](*) to reproduce S(4)N(4) with an apparent second order rate constant k(f2)' = 1.1 +/- 0.3 x 10(3) M(-1) s(-1). The crystal structure of [PPN][S(3)N(3)] was determined by X-ray crystallography indicating the solvation of the anion by 1 equiv of methanol. The generated [S(4)N(4)](-*) radical anion was detected by the Simultaneous Electrochemical Electron Paramagnetic Resonance (SEEPR) method to give: (a) [(32)S(4)(14)N(4)](-*), 9 lines, a((14)N) = 0.118 mT; (b) [(32)S(4)(15)N(4)](-*), 5 lines, a((15)N) = 0.164 mT; (c) [(33)S(4)(14)N(4)](-*), estimated a((14)N) = 0.118, a((33)S = 0.2 mT); g = 2.0008(1). Equivalence of (33)S hyperfine splittings is consistent with dynamic averaging of the C(2v) geometry in solution. High-level electronic structure calculations provide evidence for an open-shell doublet triradicaloid character to the ground state wave function of [S(3)N(3)](*).

17.
Inorg Chem ; 47(9): 3823-31, 2008 May 05.
Artigo em Inglês | MEDLINE | ID: mdl-18396861

RESUMO

DFT calculations for the group 15 radicals [PhB(mu-N(t)Bu)2]2M. (M = P, As, Sb, Bi) predict a pnictogen-centered SOMO with smaller contributions to the unpaired spin density arising from the nitrogen and boron atoms. The reactions of Li 2[PhB(mu-NR)2] (R = (t)Bu, Dipp) with PCl 3 afforded the unsolvated complex LiP[PhB(mu-N(t)Bu)2] 2 ( 1a) in low yield and ClP[PhB(mu-NDipp)2] (2), both of which were structurally characterized. Efforts to produce the arsenic-centered neutral radical, [PhB(mu-N (t) Bu) 2] 2As., via oxidation of LiAs[PhB(mu-N(t)Bu)2]2 with one-half equivalent of SO 2Cl 2, yielded the Zwitterionic compound [PhB(mu-N (t) Bu) 2As(mu-N(t)Bu)2B(Cl)Ph] (3) containing one four-coordinate boron center with a B-Cl bond. The reaction of 3 with GaCl3 produced the ion-separated salt, [PhB(mu-N(t)Bu)2] 2As (+)GaCl 4 (-) ( 4), which was characterized by X-ray crystallography. The reduction of 3 with sodium naphthalenide occurred by a two-electron process to give the corresponding anion [{PhB(mu-N(t)Bu)2} 2As] (-) as the sodium salt. Voltammetric investigations of 4 and LiAs[PhB(mu-N (t) Bu) 2] 2 ( 1b) revealed irreversible processes. Attempts to generate the neutral radical [PhB(mu-N(t)Bu)2] 2As. from these ionic complexes via in situ electrolysis did not produce an EPR-active species.

18.
Inorg Chem ; 47(2): 632-44, 2008 Jan 21.
Artigo em Inglês | MEDLINE | ID: mdl-18161967

RESUMO

The reaction of the 1,2,3,5-dithiadiazolyls (4-R-C(6)H(4)CN(2)S(2))(2) (R = Me, 2a; Cl, 2b; OMe, 2c; and CF3, 2d) and (3-NC-5-tBu-C(6)H(3)CN(2)S(2))(2) (2e) with [CpCr(CO)(3)](2) (Cp = eta(5)-C(5)H(5)) (1) at ambient temperature respectively yielded the complexes CpCr(CO)(2)(eta(2)-S(2)N(2)CC(6)H(4)R) (R = 4-Me, 3a; 4-Cl, 3b; 4-OMe, 3c; and 4-CF(3), 3d) and CpCr(CO)(2)(eta(2)-S(2)N(2)CC(6)H(3)-3-(CN)-5-(tBu)) (3e) in 35-72% yields. The complexes 3c and 3d were also synthesized via a salt metathesis method from the reaction of NaCpCr(CO)(3) (1B) and the 1,2,3,5-dithiadiazolium chlorides 4-R-C(60H(4)CN(2)S(2)Cl (R = OMe, 8c; CF(3), 8d) with much lower yields of 6 and 20%, respectively. The complexes were characterized spectroscopically and also by single-crystal X-ray diffraction analysis. Cyclic voltammetry experiments were conducted on 3a-e, EPR spectra were obtained of one-electron-reduced forms of 3a-e, and variable temperature 1H NMR studies were carried out on complex 3d. Hybrid DFT calculations were performed on the model system [CpCr(CO)(2)S(2)N(2)CH] and comparisons are made with the reported CpCr(CO)(2)(pi-allyl) complexes.

19.
Inorg Chem ; 46(14): 5596-607, 2007 Jul 09.
Artigo em Inglês | MEDLINE | ID: mdl-17552513

RESUMO

The previously unknown radical anions of unsaturated E2N4S2 ring systems (E=RC, R2NC, R2P) can be generated voltammetrically by the one-electron reduction of the neutral species and, despite half-lives on the order of a few seconds, have been unambiguously characterized by electron paramagnetic resonance (EPR) spectroelectrochemistry using a highly sensitive in situ electrolysis cell. Cyclic voltammetric studies using a glassy-carbon working electrode in CH3CN and CH2Cl2 with [nBu4N][PF6] as the supporting electrolyte gave reversible formal potentials for the [E2N4S2]0/- process in the range of -1.25 to -1.77 V and irreversible peak potentials for oxidation in the range of 0.66 to 1.60 V (vs the Fc+/0 couple; Fc=ferrocene). Reduction of the neutral compound undergoes an electrochemically reversible one-electron transfer, followed by the decay of the anion to an unknown species via a first-order (chemical) reaction pathway. The values of the first-order rate constant, kf, for the decay of all the radical anions in CH2Cl2 have been estimated from the decay of the EPR signals for (X-C6H4CN2S)2*-, where X=4-OCH3 (kf=0.04 s(-1)), 4-CH3 (kf=0.02 s(-1)), 4-H (kf=0.08 s(-1)), 4-Cl (kf=0.05 s(-1)), 4-CF3 (kf=0.05 s(-1)), or 3-CF3 (kf=0.07 s(-1)), and for [(CH3)3CCN2S]2*- (kf=0.02 s(-1)), [(CH3)2NCN2S]2*- (kf=0.05 s(-1)), and [(C6H5)2PN2S]2*- (kf=0.7 s(-1)). Values of kf for X=4-H and for [(CH3)2NCN2S]2*- were also determined from the cyclic voltammetric responses (in CH2Cl2) and were both found to be 0.05 s(-1). Possible pathways for the first-order anion decomposition that are consistent with the experimental observations are discussed. Density functional theory calculations at the UB3LYP/6-31G(d) level of theory predict the structures of the radical anions as either planar (D2h) or folded (C2v) species; the calculated hyperfine coupling constants are in excellent agreement with experimental results. Linear correlations were observed between the voltammetrically determined potentials and both the orbital energies and Hammett coefficients for the neutral aryl-substituted rings.

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