Ring opening of 2,5-didehydrothiophene: structures and rearrangements of C4H2S isomers

Electronic structures and rearrangement pathways of several C4H2S isomers are computationally investigated by methods based on coupled cluster theory and density functional theory. Six singlet C4H2S isomers lie within ca. 30 kcal/mol above butatrienethione (6), the apparent global minimum. Ethynylthioketene (7) lies only 2 kcal/mol higher in energy than cumulene 6. Two open-chain isomers, butadiynylthiol (8) and diethynyl sulfide (9), reside ca. 9 and 24 kcal/mol above 6, respectively. Lying 30 kcal/mol above 6, two cyclic singlet isomers, ethynylthiirene (10) and cyclopropenylidenemethanthione (11), are nearly degenerate in energy. Thiophene-2,5-diyl (12) lies substantially higher in energy than 6 (ca. 45 kcal/mol) and is predicted to rearrange preferentially by C-S bond cleavage, leading to thioketene 7, rather than by C-C bond cleavage, leading to diethynyl sulfide (9; retro-Bergman cyclization). Accurate spectroscopic properties of these C4H2S isomers, as well as an understanding of their rearrangement pathways, should facilitate the detection and characterization of these isomers in the laboratory and the interstellar medium.     

含碳硼烷半夹心型钴硫16电子化合物与二炔烃的反应性研究

含双硫取代碳硼烷二齿配体的半夹心型钴16电子化合物CpCo[S2C2(B10H10)](Co16e)分别与1,4-二乙炔基苯(L1)、(S)-2,2′-二乙酰氧基-6,6′-二乙炔基-1,1′-联萘(L2)、2-溴-5-乙炔基噻吩(L3)和2,5-二乙炔基噻吩(L4)反应,分别得到18电子单核化合物CpCo(S2C2B10H9)(H2CCPhC≡CH)(1),CpCo(S2C2B10H9)[H2CC(C24H16O4)C≡CH](2),CpCo(S2C2B10H9)[H2CC(C4H2S)Br](3),和CpCo(S2C2B10H9)[H2CC(C4H2S)C≡CH](4)。化合物1～4的结构中都发生了金属诱导B-H键活化并生成了新的C-B键。在Co16e与L4的反应中,还得到了两分子炔烃以头对头二聚插入到金属中心的18电子化合物CpCo(S2C2B10H9)[HC≡C(C4H2S)C=CH-CH=C(C4H2S)C≡CH](5)。上述化合物通过NMR、IR、MS、元素分析等方法进行表征。     

Regioselective coupling of pentafluorophenyl substituted alkynes: mechanistic insight into the zirconocene coupling of alkynes and a facile route to conjugated polymers bearing electron-withdrawing pentafluorophenyl substituents

The reaction of Cp(2)ZrCl(2) with 2 equiv of BuLi at -78 degrees C, followed by the addition of an unsymmetrical tetra- or pentafluorophenyl substituted alkyne R(1)C[triple bond]CAr(f) (R(1), Ar(f) = (CH(2))(4)Me, p-C(6)F(4)H; Me, p-C(6)F(4)H; Ph, C(6)F(5)), resulted in regioselective couplings of these alkynes to zirconacyclopentadienes in which the Ar(f) substituents preferentially adopt the 3,4-positions (beta beta) of the zirconacyclopentadiene ring. With Cp(2)Zr(py)(Me(3)SiC[triple bond]CSiMe(3)) as the zirconocene reagent, the couplings could be carried out at room temperature; however, at higher temperatures significant quantities of the 2,4-fluoroaryl substituted (alpha beta) isomers were also formed. None of the conditions employed produced the 2,5-fluoroaryl substituted (alpha alpha) isomers. These fluoroaryl-substituted zirconacyclopentadienes were readily converted to butadienes via reactions with acids. The zirconacyclopentadiene Cp(2)ZrC(4)-2,5-Ph(2)-3,4-(C(6)F(5))(2), which resulted from the coupling of PhC[triple bond]C(C(6)F(5)), was converted to the corresponding thiophene by reaction with S(2)Cl(2), and to an arene by reaction with MeO(2)CC[triple bond]CCO(2)Me/CuCl. Mechanistic studies on zirconocene couplings of (p-CF(3)C(6)H(4))C[triple bond]C(p-MeC(6)H(4)) indicate that the observed regioselectivities are determined by an electronic factor that controls the orientation of at least one of the two alkynes as they are coupled. Additionally, these studies suggest an unsymmetrical transition state for the zirconocene coupling of alkynes, and this is supported by DFT calculations. The reaction of [(C(6)F(5))C[triple bond]CCH(2)](2)CH(2) with Cp(2)Zr(py)(Me(3)SiC[triple bond]CSiMe(3)) resulted in a zirconacyclopentadiene in which the pentafluorophenyl substituents have been forced into the 2,5-positions (alpha alpha). Zirconocene coupling of the diyne (C(6)F(5))C[triple bond]C-1,4-C(6)H(4)-C[triple bond]C(C(6)F(5)) provided a route to conjugated polymers bearing electron-withdrawing pentafluorophenyl groups.     

The unexpected desulfurization of 4-aminothiophenols

Thermolysis of 4-aminophenyl benzyl sulfide at 523 K in the hydrogen donor solvent (HDS), 9,10-dihydroanthracene (AnH2), gave 4-aminothiophenol and toluene as the predominant products of the homolytic S-C bond cleavage. Under these conditions, a portion of the 4-aminothiophenol was desulfurized to aniline with first-order kinetics and with a rate constant estimated by kinetic modeling to be 7.0x10(-6) s-1. Starting with 4-NH2C6H4SH at 523 K, it was found that sulfur loss was more efficient in the non-HDSs, anthracene and hexadecane, than in AnH2. Under similar (competitive) reaction conditions, YC6H4SHs with Y=H, 4-CN, and 3-CF3 were completely inert; with Y=4-CH3O, there was some very minor desulfurization, whereas with Y=4-N(CH3)2 and 4-N(CH3)(H), the sulfur extrusions were as fast as that for Y=4-NH2. We tentatively suggest that this apparently novel reaction is a chain process initiated by the bimolecular formation of diatomic sulfur, S2, followed by a reversible addition of ground state, triplet 3S2 to the thiol sulfur atom, 4-NH2C6H4S upward arrow(SS upward arrow)H, and insertion into the S-H bond, 4-NH2C6H4SSSH. In a cascade of reactions, aniline and S8 are formed with the chains being terminated by reaction of 4-NH2C6H4S upward arrow(SS upward arrow)H with 4-NH2C6H4SH. Such a reaction mechanism is consistent with the first-order kinetics. That this reaction is primarily observed with 4-YC6H4SH having Y=N(CH3)2, N(CH3)(H), and NH2 is attributed to the fact that these compounds can exist as zwitterions.     

DFT study on the reaction mechanisms of polyfluorosulfonate ester with F

Gas-phase reaction of C(1)F₃S(2)O₂O(3)C(4)H₂C(5)F₃ and F⁻(16) is investigated using DFT method. The geometries of various stationary points and their relative energies are obtained from 6-31+G*, 6-311G**, and 6-311++G** levels. In the S_N2(C) reaction leading to the cleavage of the C(4)–O(3) bond, the reaction complex results from attacking of F⁻ at a hydrogen atom H11 attached to carbon atom C(4). Afterward, F⁻ is attacking the atom C(4) from the backside of the atom O(3) with the help of the neighboring effect, and meanwhile a multi-membered ring, F(16)–H(11)–C(4)–C(5)–F(16), is being formed. The S_N2(C) reaction is irreversible. On the contrary, the S_N2(S) reaction leading to the cleavage of the S(2)–O(3) bond is reversible, and it is initiated by attacking of F⁻ at the atom S(2) from the backside of the atom O(3). The products of the reaction CF₃SO₃CH₂CF₃ +F⁻ should be, thermodynamically, controlled due to the reversibility of the S_N2(S) reaction, and those result, chemospecifically, from the cleavage of the C–O bond. At last, the SCRF calculations confirm that the solvent effect is preferable to the S_N2(C) reaction.     

C-O bond cleavage of benzophenone substituted by 4-CH2OR (R = C6H5 and CH3) with stepwise two-photon excitation

The C-O bond cleavage from benzophenone substituted with 4-CH2OR (p-BPCH2OR, 1-3), such as p-phenoxymethylbenzophenone (1, R= C6H5) and p-methoxymethylbenzophenone (2, R= CH3), occurred by a stepwise two-photon excitation during two-color, two-laser flash photolysis. On the other hand, no C-O bond cleavage occurred from p-hydroxymethylbenzophenone (3, R = H). The first 355-nm laser excitation of 1-3 generates p-BPCH2OR in the lowest triplet excited state (T1) which has an absorption at 532 nm. When p-BPCH2OR(T1) is excited with the second 532-nm laser to p-BPCH2OR in the higher triplet excited state (T(n)), the C-O bond cleavage occurred within the laser flash duration of 5 ns. The quantum yields of the C-O bond cleavage during the second 532-nm laser irradiation were found to be 0.015 +/- 0.007 and 0.007 +/- 0.003 for 1 and 2, respectively. Although these values are low, the diminishing 1(T1) or 2(T1) was found to convert, in almost 100% yield, to phenoxyl (C6H5O*) and p-benzoylbenzyl (BPCH2*) radicals or methoxyl (CH3O*) and BPCH2* radicals, respectively. The T(n) excitation energy, the energy barrier along the potential surface between the T(n) states and product radicals, and delocalization of the T(n) state molecular orbital including BP and CH2OR (R = C6H5, CH3, H) moieties are important factors for the occurrence of the C-O bond cleavage. It is found that the C-O bond cleavage and production of free radicals, such as BPCH2*, C6H5O*, and CH3O*, can be performed by a stepwise two-photon excitation. The present study is an example in which the chemical reactions can be selectively initiated from the T(n) state but not from the S1 and T1 states.     

Organobismuth(III) Derivatives of Sterically Hindered Bifunctional Tetradentate Schiff Bases: Synthesis and Spectroscopic Characterization

The equimolar reactions of Ph 3 Bi with the bifunctional tetradentate Schiff bases proceed with cleavage of two Bi--C bond of Ph 3 Bi and result in the formation of phenylbismuth(III) derivatives PhBi[RC(NC 6 H 4 S)CH 2 (NC 6 H 4 S)CCOOCH 3 ] where R = C 6 H 5 , 4-ClC 6 H 4 ,4-BrC 6 H 4 , and 4-CH 3 C 6 H 4 . Physico-chemical, IR, and NMR ( 1 H and 13 C) spectral studies have been carried out to investigate the structural aspect of these derivatives which reveal a penta coordination around the central Bi atom.     

Reactivity of the 16e (p-cymene)Ru half-sandwich complex containing a chelating 1,2-dicarba-closo-dodecaborane-1,2-dithiolate ligand towards diynes

The reactions of the 16e half-sandwich complex (p-cymene)Ru(S(2)C(2)B(10)H(10)) (Ru16e) with 1,4-diethynylbenzene (L1), 3',6-diethynyl-1,1'-binaphthyl-2,7'-diyl diacetate (L2), 2-bromo-5-ethynylthiophene (L3) and 2,5-diethynylthiophene (L4) lead to 18e mononuclear complexes (p-cymene)Ru(S(2)C(2)B(10)H(9))(H(2)CCPhC≡CH) (1), (p-cymene)Ru(S(2)C(2)B(10)H(9))[H(2)CC(C(24)H(16)O(4))C≡CH] (2), (p-cymene)Ru(S(2)C(2)B(10)H(9)) [H(2)CC(C(4)H(2)S)Br] (3) and (p-cymene)Ru(S(2)C(2)B(10)H(9)) [H(2)CC(C(4)H(2)S)C≡CH] (4), respectively. In all of them, metal-induced B-H activation has occurred, which leads to a stable Ru-B bond, and the structures take a cisoid arrangement. Only in the case of L4, the binuclear complexes [(p-cymene)Ru(S(2)C(2)B(10)H(9))](2)[H(2)CC(C(4)H(2)S)CCH(2)] (5a and 5b) are observed, which are conformational isomers generated by the differing orientations of the p-cymene unit. 4 can be readily converted to the complex (p-cymene)Ru(S(2)C(2)B(10)H(9))[H(2)CC(C(4)H(2)S)COCH(3)] (6) in the presence of silica and H(2)O. All of these products 1-6 were characterized by NMR, IR, elemental analysis and mass spectrometry. The structures of 1, 3, and 5a were also determined by single-crystal X-ray diffraction analysis.     

Structural and solvent effects on the C-S bond cleavage in aryl triphenylmethyl sulfide radical cations

Steady-state and laser flash photolysis (LFP) studies of a series of aryl triphenylmethyl sulfides [1, 3,4-(CH(3)O)(2)-C(6)H(3)SC(C(6)H(5))(3); 2, 4-CH(3)O-C(6)H(4)SC(C(6)H(5))(3); 3, 4-CH(3)-C(6)H(4)SC(C(6)H(5))(3); 4, C(6)H(5)SC(C(6)H(5))(3); and 5, 4-Br-C(6)H(4)SC(C(6)H(5))(3)] has been carried out in the presence of N-methoxyphenanthridinium hexafluorophosphate in CH(3)CN, CH(2)Cl(2), CH(2)Cl(2)/CH(3)CN, and CH(2)Cl(2)/CH(3)OH mixtures. Products deriving from the C-S bond cleavage in the radical cations 1(?+)-5(?+) have been observed in the steady-state photolysis experiments. Time-resolved LFP showed first-order decay of the radical cations accompanied by formation of the triphenylmethyl cation. A significant decrease of the C-S bond cleavage rate constants was observed by increasing the electron-donating power of the arylsulfenyl substituent, that is, by increasing the stability of the radical cations. DFT calculations showed that, in 2(?+) and 3(?+), charge and spin densities are mainly localized in the ArS group. In the TS of the C-S bond cleavage an increase of the positive charge in the trityl moiety and of the spin density on the ArS group is observed. The higher delocalization of the charge in the TS as compared to the initial state is probably at the origin of the observation that the C-S bond cleavage rates decrease by increasing the polarity of the solvent.     

C-H Bond activation and C-C bond formation in the reaction of 2,5-dimethylthiophene with TpMe2Ir compounds

The bulky 2,5-dimethylthiophene (2,5-Me2T) reacts at 60 degrees C with TpMe2Ir(C2H4)2 to give a mixture of two TpMe2Ir(III) hydride products, 3 and 4, that contain in addition a thienyl (3) or a thienyl-derived ligand (4). For the generation of 3 only sp2 C-H activation is needed, but the formation of 4 requires also the activation of an sp3 C-H bond and the formation of a new C-C bond (between vinyl and thienyl fragments). In the presence of 2,5-Me2T, compound 4 reacts further to produce a complex thiophenic structure (5, characterized by X-ray methods) that derives formally from two molecules of 2,5-Me2T and a vinyl fragment. Compounds 3-5 can be readily protonated by [H(OEt2)2][BAr'4](Ar'= 3,5-C6H3(CF3)2), with initial generation of carbene ligands (in the case of 3 and 5) as a consequence of H+ attack at the beta-carbon of the Ir-thienyl unit. Free, substituted thiophenes, derived from the original 2,5-Me2T, may be isolated in this way.     

Synthesis, structural, spectroscopic, and electrochemical characterization of high oxidation state diruthenium complexes containing four identical unsymmetrical bridging ligands

Six Ru2(6+) derivatives of the form Ru2(L)4(C[triple bond]CC6H5)(2), where L = 2-Fap, 2,3-F(2)ap, 2,4-F(2)ap, 2,5-F(2)ap, 3,4-F(2)ap, or 2,4,6-F(3)ap, are synthesized and characterized as to their electrochemical, spectroscopic, and/or structural properties. These compounds are synthesized from a reaction between LiC[triple bond]CC6H5 and Ru2(L)4Cl. Two of the investigated complexes exist in a (4,0) isomeric form while four adopt a (3,1) geometric conformation. These two series of geometric isomers are compared with previously characterized (4,0) Ru2(ap)4(C[triple bond]CC6H5)(2), (4,0) Ru2(F5ap)4(C[triple bond]CC6H5)(2), and (3,1) Ru2(F5ap)4(C[triple bond]CC6H5)(2). The overall data on the nine compounds thus provide an opportunity to systematically examine how the electrochemical and structural properties of these Ru2(6+) complexes vary with respect to isomer type and electronic properties of the bridging ligands.     

Acylation of 2,5-dimethoxycarbonyl[60]fulleropyrrolidine and synthesis of its multifullerene derivatives

2,5-Dimethoxycarbonyl[60]fulleropyrrolidine (1) is acylated with various chlorocarbonyl compounds to give fullerene derivatives with the general formula C(60)(MeOOCCH)(2)NC(O)R, R = (CH(2))(5)Br, (CH(2))(8)C(O)Cl (3), (CH(2))(4)C(O)Cl, or cis-C(6)H(4)(C(O)Cl. The monoacylated sebacoyl derivative 3 readily reacts with alcohols and amines such as methanol, diethylamine, glycine methyl ester, and aza-18-crown-6 through the remaining chlorocarbonyl group. Chromatography of 3 on silica gel converts it into the corresponding acid C(60)(MeOOCCH)(2)NC(O)(CH(2))(8)COOH (4). Treating 4 with PCl(5) regenerates the precursor 3 quantitatively. Piperazine reacts with 4 in the presence of DCC and BtOH to form a bisfullerene derivative in which two sebacoyl chains and the piperazine act as the bridge between two molecules of 1. Other molecules with multifunctional groups react with 4 similarly to form multifullerene derivatives. NMR data indicate that the rotation of the relatively bulky phthaloyl group is hindered around the amide bond N [bond] C(O), the rotation barrier of which is 15.06 kcal/mol. The relative stereochemistry of the 2,5-dimethoxycarbonyl groups is established by (1)H NMR spectra and further confirmed by resolution of the enantiomeric 2,5-trans-isomer of the starting material 1.     

Direct detection of products from the pyrolysis of 2-phenethyl phenyl ether

The pyrolysis of 2-phenethyl phenyl ether (PPE, C(6)H(5)C(2)H(4)OC(6)H(5)) in a hyperthermal nozzle (300-1350 °C) was studied to determine the importance of concerted and homolytic unimolecular decomposition pathways. Short residence times (<100 μs) and low concentrations in this reactor allowed the direct detection of the initial reaction products from thermolysis. Reactants, radicals, and most products were detected with photoionization (10.5 eV) time-of-flight mass spectrometry (PIMS). Detection of phenoxy radical, cyclopentadienyl radical, benzyl radical, and benzene suggest the formation of product by the homolytic scission of the C(6)H(5)C(2)H(4)-OC(6)H(5) and C(6)H(5)CH(2)-CH(2)OC(6)H(5) bonds. The detection of phenol and styrene suggests decomposition by a concerted reaction mechanism. Phenyl ethyl ether (PEE, C(6)H(5)OC(2)H(5)) pyrolysis was also studied using PIMS and using cryogenic matrix-isolated infrared spectroscopy (matrix-IR). The results for PEE also indicate the presence of both homolytic bond breaking and concerted decomposition reactions. Quantum mechanical calculations using CBS-QB3 were conducted, and the results were used with transition state theory (TST) to estimate the rate constants for the different reaction pathways. The results are consistent with the experimental measurements and suggest that the concerted retro-ene and Maccoll reactions are dominant at low temperatures (below 1000 °C), whereas the contribution of the C(6)H(5)C(2)H(4)-OC(6)H(5) homolytic bond scission reaction increases at higher temperatures (above 1000 °C).     

Mechanism of reversible alkyne coupling at zirconocene: ancillary ligand effects

The mechanism of reversible alkyne coupling at zirconium was investigated by examination of the kinetics of zirconacyclopentadiene cleavage to produce free alkynes. The zirconacyclopentadiene rings studied possess trimethylsilyl substituents in the alpha-positions, and the ancillary Cp2, Me2C(eta(5)-C5H4)2, and CpCp* (Cp* = eta(5)-C5Me5) bis(cyclopentadienyl) ligand sets were employed. Fragmentation of the zirconacyclopentadiene ring in Cp2Zr[2,5-(Me3Si)2-3,4-Ph2C4] with PMe3, to produce Cp2Zr(eta(2)-PhC[triple bond]CSiMe3)(PMe3) and free PhC[triple bond]CSiMe3, is first-order in initial zirconacycle concentration and zero-order in incoming phosphine (k(obs) = 1.4(2) x 10(-5) s(-1) at 22 degrees C), and the activation parameters determined by an Eyring analysis (DeltaH(double dagger) = 28(2) kcal mol(-1) and DeltaS(double dagger) = 14(4) eu) are consistent with a dissociative mechanism. The analogous reaction of the ansa-bridged complex Me2C(eta(5)-C5H4)2Zr[2,5-(Me3Si)2-3,4-Ph2C4] is 100 times faster than that for the corresponding Cp2 complex, while the corresponding CpCp* complex reacts 20 times slower than the Cp2 derivative. These rates appear to be largely influenced by the steric properties of the ancillary ligands.     

Palladium dimethylsilanedithiolato complex: a precursor for Ti-Pd and Ti-Pd2 heterometallic complexes

The silanedithiolato complex Pd(S2SiMe2)(PEt3)2 1 reacted with (C5H5)TiCl3 and TiCl4(thf)2 to produce the heterometallic clusters (C5H5)TiCl(mu-S)2Pd(PEt3)2 2 and TiCl2(S)(mu-S)2Pd2(PEt3)4 3 along with silicon-sulfur bond cleavage, respectively.     

Photochemical and thermal reactions of intermediates in the phenylnitrene rearrangement inside a hemicarcerand

Broadband irradiation (lambda > 320 nm) of hemicarceplex H(.)1 between -74 degrees C and -84 degrees C, produces encapsulated didehydroazepine (2), triplet phenylnitrene ((3)PN), 2-azabicyclo[3.2.0]hepta-1,3,6-triene (6), and 4-azaspiro[2.4]hepta-1,4,6-triene (7). The highly strained anti-Bredt imine 6 is formed from 2 via a photochemical four-electron electrocyclization. Under the irradiation conditions, 6 rearranges further to azaspirene 7. In addition, 6 thermally rearranges to 7 via a 1,5-sigmatropic shift (DeltaG(267K) = 20.0 +/- 0.5 kcal/mol), yielding a final equilibrium composed of [7]/[6] = 5 at room temperature. The observation of a photochemical rearrangement of 2 to 6 contrasts earlier results of narrow band irradiations (lambda = 334 nm) of matrix-isolated 2, which gave (3)PN (Hayes, J. C.; Sheridan, R. S. J. Am. Chem. Soc. 1990, 112, 5879-5881). Encapsulated (3)PN is remarkably stable due to the prevention of its dimerization by the surrounding hemicarcerand. Above 255 K, it slowly decays with a rate constant k = 10(7.7+/-0.4) s(-1) x exp {(13300 +/- 500 cal/mol)/RT}. The isolation of substantial amounts of a hemicarcerand lacking one acetal spanner suggests that (3)PN decays preferentially by inserting into an inward-pointing acetal C-H bond of H.     

Synthesis and charge/discharge properties of polyacetylenes carrying 2,2,6,6-tetramethyl-1-piperidinoxy radicals

The 2,2,6,6-tetramethyl-1-piperidinoxy (TEMPO)-containing acetylenic monomers HC[triple bond]CC(6)H(3)-p,m-(CONH-4-TEMPO)(2) (1), HC[triple bond]CC(6)H(3)-p,m-(COO-4-TEMPO)(2) (2), (S,S,S,S)-HC[triple bond]CC(6)H(3)-p,m-[CO-NHCH{COO-(4-TEMPO)}CH(2)COO-(4-TEMPO)](2) (3), (S,S)-HC[triple bond]CC(6)H(4)CO-NHCH{COO-(4-TEMPO)}CH(2)COO-(4-TEMPO) (4), HC[triple bond]CC(6)H(4)-p-OCO-4-TEMPO (5), HC[triple bond]CCH(2)C(CH(3))(CH(2)OCO-4-TEMPO)(2) (6), HC[triple bond]CCH(2)NHCO-4-TEMPO (7), and HC[triple bond]CCH(2)OCO-4-TEMPO (8) were polymerized to afford novel polymers containing the TEMPO radical at high densities. Monomers 1, 3-6, and 8 provided polymers with average molecular weights of 10 000-136 500 in 62-99 % yield in the presence of a rhodium catalyst, whereas monomers 2 and 7 gave insoluble polymers in 100 % yield. The formed polymers were thermally stable up to approximately 274 degrees C according to thermogravimetric analysis (TGA). All the TEMPO-containing polymers demonstrated reversible charge/discharge processes, whose discharge capacities were 21.3-108 A h kg(-1). In particular, the capacity of poly(1)-, poly(4)-, and poly(5)-based cells reached 108, 96.3, and 89.3 A h kg(-1), respectively, which practically coincided with their theoretical values.     

Photosensitized oxidation of alkyl phenyl sulfoxides. C-S bond cleavage in alkyl phenyl sulfoxide radical cations

The 3-cyano-N-methylquinolinium perchlorate (3-CN-NMQ(+)ClO4(-))-photosensitized oxidation of phenyl alkyl sulfoxides (PhSOCR1R2R3, 1, R1 = R2 = H, R3 = Ph; 2, R1 = H, R2 = Me, R3 = Ph; 3, R1 = R2 = Ph, R3 = H; 4, R1 = R2 = Me, R3 = Ph; 5, R1 = R2 = R3 = Me) has been investigated by steady-state irradiation and nanosecond laser flash photolysis (LFP) under nitrogen in MeCN. Steady-state photolysis showed the formation of products deriving from the heterolytic C-S bond cleavage in the sulfoxide radical cations (alcohols, R1R2R3COH, and acetamides, R1R2R3CNHCOCH3) accompanied by sulfur-containing products (phenyl benzenethiosulfinate, diphenyl disulfide, and phenyl benzenethiosulfonate). By laser irradiation, the formation of 3-CN-NMQ(*) (lambda(max) = 390 nm) and sulfoxide radical cations 1(*+) , 2(*+), and 5(*+) (lambda(max) = 550 nm) was observed within the laser pulse. The radical cations decayed by first-order kinetics with a process attributable to the heterolytic C-S bond cleavage leading to the sulfinyl radical and an alkyl carbocation. The radical cations 3(*+) and 4(*+) fragment too rapidly, decaying within the laser pulse. The absorption band of the cation Ph2CH(+) (lambda(max) = 440 nm) was observed with 3 while the absorption bands of 3-CN-NMQ(*) and PhSO(*) (lambda(max) = 460 nm) were observed just after the laser pulse in the LFP experiment with 4. No competitive beta-C-H bond cleavage has been observed in the radical cations from 1-3. The C-S bond cleavage rates were measured for 1(*+), 2(*+), and 5(*+). For 3(*+) and 4(*+), only a lower limit (ca. >3 x 10(7) s(-1)) could be given. Quantum yields (Phi) and fragmentation first-order rate constants (k) appear to depend on the structure of the alkyl group and on the bond dissociation free energy (BDFE) of the C-S bond of the radical cations determined by a thermochemical cycle using the C-S BDEs for the neutral sulfoxides 1-5 obtained by DFT calculations. Namely, Phi and k increase as the C-S BDFE becomes more negative, that is in the order 1 < 5 < 2 < 3, 4, which is also the stability order of the alkyl carbocations formed in the cleavage. An estimate of the difference in the C-S bond cleavage rate between sulfoxide and sulfide radical cations was possible by comparing the fragmentation rate of 5(*+) (1.4 x 10(6) s(-1)) with the upper limit (10(4) s(-1)) given for tert-butyl phenyl sulfide radical cation (Baciocchi, E.; Del Giacco, T.; Gerini, M. F.; Lanzalunga, O. Org. Lett. 2006, 8, 641-644). It turns out that sulfoxide radical cations undergo C-S bond breaking at a rate at least 2 orders of magnitude faster than that of corresponding sulfide radical cations.     

Oxidative Cleavage of C=S and P=S Bonds at an AlI Center: Preparation of Terminally Bound Aluminum Sulfides

The treatment of cyclic thioureas with the aluminum(I) compound NacNacAl ( 1 ; NacNac=[ArNC(Me)CHC(Me)NAr]^?, Ar=2,6‐Prⁱ₂C₆H₃) resulted in oxidative cleavage of the C=S bond and the formation of 3 and 5 , the first monomeric aluminum complexes with an Al=S double bond stabilized by N‐heterocyclic carbenes. Compound 1 also reacted with triphenylphosphine sulfide in a similar manner, which resulted in cleavage of the P=S bond and production of the adduct [NacNacAl=S(S=PPh₃)] ( 8 ). The Al=S double bond in 3 can react with phenyl isothiocyanate to furnish the cycloaddition product 9 and zwitterion 10 as a result of coupling between the liberated carbene and PhN=C=S. All novel complexes were characterized by multinuclear NMR spectroscopy, and the structures of 5 , 9 , and 10 were confirmed by X‐ray diffraction analysis. The nature of the Al=S bond in 5 was also probed by DFT calculations.     

C-C versus C-H bond activation of alkynes by early second-row transition metal atoms

The reactions of Y (a2D), Zr (a3F), Nb (a6D), Mo (a7S), and electronically excited-state Mo* (a5S) with propyne (methylacetylene) and 2-butyne (1,2-dimethylacetylene) were investigated using crossed molecular beams. For all of the metals studied, reactions with propyne led to H2 elimination, forming MC3H2. For Y + propyne, C-C bond cleavage forming YCCH + CH3 also was observed, with an energetic threshold in good agreement with an earlier determination of D0(Y-CCH). For Y + 2-butyne, three reactive channels were observed: YC4H4 + H2, YC3H3 + CH3, and YC3H2 + CH4. The C-C bond cleavage products accounted for 21 and 27% of the total products at Ecoll = 69 and 116 kJ/mol, respectively. For Zr and Nb reactions with 2-butyne, competition between H2 and CH4 elimination was observed, with C-C bond cleavage accounting for 12 and 4% of the total product signal at Ecoll = 71 kJ/mol, respectively. For reactions of Mo and Mo* with 2-butyne, only H2 elimination was observed. The similarity between reactions involving two isomeric species, propyne and allene, suggests that H atom migration is facile in these systems.