Molecular precursors to gallium oxide thin films

The donor-functionalised alkoxides [Et(2)Ga(OR)](2)(R = CH(2)CH(2)NMe(2)(1), CH(CH(2)NMe(2))(2)(2), CH(2)CH(2)OMe (3), CH(CH(3))CH(2)NMe(2)(4), C(CH(3))(2)CH(2)OMe (5)) were synthesised by the 1:1 reaction of Et(3)Ga with ROH in hexane or dichloromethane at room temperature. Reaction of Et(3)Ga with excess ROH in refluxing toluene resulted in the isolation of a 1:1 mixture of [Et(2)Ga(OR)](2) and the ethylgallium bisalkoxide [EtGa(OR)(2)](R = CH(2)CH(2)NMe(2)(6) or CH(CH(3))CH(2)NMe(2)(7)). X-ray crystallography showed that compound 6 is monomeric and this complex represents the first structurally characterised monomeric gallium bisalkoxide. Homoleptic gallium trisalkoxides [Ga(OR)(3)](2) were prepared by the 1:6 reaction of [Ga(NMe(2))(3)](2) with ROH (R = CH(2)CH(2)NMe(2)(8), CH(CH(3))CH(2)NMe(2)(9), C(CH(3))(2)CH(2)OMe (10)). The decomposition of compounds 1, 4, 5 and 8 were studied by thermal gravimetric analysis. Low pressure CVD of 1 and 5 resulted in the formation of thin films of crystalline Ga(2)O(3).     

Synthesis and Characterization of a New Alkenyldecaborane and Alkenyl Monocarbon Carboranes

Decaborane(14) reacts with 1-(CH(3))(3)SiC&tbd1;CC(4)H(9) in the presence of dimethyl sulfide to give the new alkenyldecaborane 5-(S(CH(3))(2))-6-[(CH(3))(3)Si(C(4)H(9))C=CH]B(10)H(11) (I). Crystal data for 5-(S(CH(3))(2))-6-[(CH(3))(3)Si(C(4)H(9))C=CH]B(10)H(11): space group P2(1)/n, monoclinic, a = 9.471(1) ?, b = 13.947(3) ?, c = 17.678(3) ?, beta = 100.32(1) degrees. A total of 3366 unique reflections were collected over the range 2.0 degrees /= 3sigma(F(o)(2)) and were used in the final refinement. R(F)() = 0.083; R(w)(F)() = 0.094. The single-crystal X-ray structure of 5-(S(CH(3))(2))-6-[((CH(3))(3)Si)(2)C=CH]B(10)H(11) (A) is also reported. Crystal data for 5-(S(CH(3))(2))-6-[((CH(3))(3)Si)(2)C=CH]B(10)H(11): space group, P2(1)2(1)2(1), orthorhombic, a = 9.059 (3) ?, b = 12.193(4) ?, c = 21.431(3) ?. A total of 4836 unique reflections were collected over the range 6 degrees /= 3sigma(F(o)(2)) and were used in the final refinement. R(F)() = 0.052; R(w)(F)() = 0.059. The reactions of 5-(S(CH(3))(2))6-[(CH(3))(3)Si(C(4)H(9))C=CH]B(10)H(11) and 5-(S(CH(3))(2))6-[((CH(3))(3)Si)(2)C=CH]B(10)H(11) with a variety of alkyl isocyanides were investigated. All of the alkenyl monocarbon carboranes reported are the result of incorporation of the carbon atom from the isocyanide into the alkenyldecaborane framework and reduction of N&tbd1;C bond to a N-C single bond. The characterization of these compounds is based on (1)H and (11)B NMR data, IR spectroscopy, and mass spectrometry.     

Pentamethylcyclopentadienyl-iridium(III) complexes with pyridylamino ligands: synthesis and applications as asymmetric catalysts for Diels-Alder reactions

Reaction of the dimer [(Cp*IrCl)2(P-Cl)2] with chiral pyridylamino ligands (pyam, L1-L5) in the presence of NaSbF6 gave complexes [Cp*IrCl(pyam)][SbF6] 1-5 as diastereomeric mixtures, which have been fully characterised, including the X-ray molecular structure determination of the complexes (S(Ir),R(N),R(C))-[Cp*IrClL1][SbF6] 1a and (R(Ir),S(N),S(C))-[Cp*IrClL5][SbF6] 5a. Treatment of these cations with AgSbF6 affords the corresponding aqua species [Cp*Ir(pyam)(H2O)][SbF6]2 6-10 which have been also fully characterised. The molecular structure of the complex (S(Ir),R(N),R(C))-[Cp*IrL,(H2O)][SbF6]2 6 has been determined by X-ray diffractometric methods. The aqua complexes [Cp*Ir(pyam)(H2O)][SbF6]2 (6, pyam = L2 (7), L3 (8)) evolve to the cyclometallated species [Cp*Ir{kappa3(N,N',C)-(R)-(C6H4)CH(CH3)NHCH2C5NH4}][SbF6] (11), [Cp*Ir{kappa3(N,N',C)-(R)-(C10H6)CH(CH3)-NHCH2C5NH4)}][SbF6] (12), and [Cp*Ir{kappa3(N,N',C)-(R)-(C10H6)CH(CH3)NHCH2C9NH6)}][SbF6] (13) respectively, via intramolecular activation of an ortho C-H aryl bond. Complexes 6-10 are enantioselective catalysts for the Diels-Alder reaction between methacrolein and cyclopentadiene. Reaction occurs rapidly at room temperature with good exo : endo selectivity (from 81 : 19 to 98 : 2) and moderate enantioselectivity (up to 72%). The involved intermediate Lewis acid-dienophile compounds [Cp*Ir(pyam)(methacrolein)][SbF]2 (pyam = L4 (14), L5 (15)) have been isolated and characterised.     

Tripodal bis(imidazole) thioether copper(I) complexes: mimics of the Cu(M) site of copper hydroxylase enzymes

Tripodal bis(imidazole) thioether ligands, (N-methyl-4,5-diphenyl-2-imidazolyl)2C(OR)C(CH3)2SR' (BIT(OR,SR'); R = H, CH3; R' = CH3, C(CH3)3, C(C6H5)3), have been prepared, offering the same N2S donor atom set as the CuM binding site of the hydroxylase enzymes, dopamine beta hydroxylase and peptidylglycine hydroxylating monooxygenase. Isolable copper(I) complexes of the type [(BIT(OR,SMe))Cu(CO)]PF6 (3a and 3b) are produced in reactions of the respective tripodal ligands 1a (R = H) and 1b (R = Me) with [Cu(CH3CN)4]PF6 in CH2Cl2 under CO (1 atm); the pyramidal structure of 3a has been determined crystallographically. The infrared (IR) nu(CO)'s of 3a and 3b (L = CO) are comparable to those of the Cu(M)-carbonylated enzymes, indicating similar electronic character at the copper centers. The reaction of [(BIT(OH,SMe))Cu(CH3CN)]PF6 (2a) with dioxygen produces [(BIT(O,SOMe))2Cu2(DMF)2](PF6)2 (4), whose X-ray structure revealed the presence of bridging BIT-alkoxo ligands and terminal -SOMe groups. In contrast, oxygenation of 2b (R = Me) affords crystallographically defined [(BIT(OMe,SMe))2Cu2(mu-OH)2](OTf)2 (5), in which the copper centers are oxygenated without accompanying sulfur oxidation. Complex 5 in DMF is transformed into five-coordinate, mononuclear [CuII(BIT(OMe,SMe))(DMF)2](PF6)2 (6). The sterically hindered BIT(OR,SR') ligands 9 and 10 (R' = t-Bu; R = H, Me) and 11 and 12 (R' = CPh3; R = H, Me) were also prepared and examined for copper coordination/oxygenation. Oxygenation of copper(I) complex 13b derived from the BIT(OMe,SBu-t) ligand is slow, relative to 2b, producing a mixture of (BIT(OMe,SBu-t))2Cu2(mu-OH)2-type complexes 14b and 15b in which the -SBu-t group is uncoordinated; one of these complexes (15b) has been ortho-oxygenated on a neighboring aryl group according to the X-ray analysis and characterization of the free ligand. Oxygenation of the copper(I) complex derived from BIT(OMe,SCPh3) ligand 12 produces a novel dinuclear disulfide complex, [(BIT(OMe,S)2Cu2(mu-OH)2](PF6)2 (17), which is structurally characterized. Reactivity studies under anaerobic conditions in the presence of t-BuNC indicate that 17 is the result of copper(I)-induced detritylation followed by oxygenation of a highly reactive copper(I)-thiolate complex.     

Versatility of dithiophosphates in the syntheses of copper(I) complexes with bis(diphenylphosphino)alkanes: abstraction of chloride from dichloromethane

Reactions of [Cu(CH(3)CN)(4)]X (X = PF(6), BF(4)) with bis(diphenylphosphino)methane (dppm = Ph(2)PCH(2)PPh(2)) and ammonium dialkyldithiophosphates, (NH(4))[S(2)P(OR)(2)] (R = Et, (i)Pr), yield a series of novel Cu(I) polynuclear complexes, trinuclear [Cu(3)(mu-dppm)(3)(mu(3)-Cl){S(2)P(OEt)(2)}] (PF(6)) 1 and [Cu(3)(mu-dppm)(2){S(2)P(OR)(2)}(2)](PF(6)) (R = Et, 2; (i)Pr, 3), tetranuclear [Cu(4)(mu-dppm)(2) {S(2)P(OEt)(2)}(4)] 4, and hexanuclear [Cu(6)(mu-dppm)(2)(mu(4)-Cl){S(2)P(O(i)()Pr)(2)}(4)](BF(4)) 5. Similarly, the reaction of [Cu(2)(mu-L-L)(2)(CH(3)CN)(2)](PF(6))(2) (L-L, dppm, dppe = Ph(2)PCH(2)CH(2)PPh(2)) with (NH(4))[S(2)P(OR)(2)] yields dinuclear [Cu(2)(mu-dppm)(2){S(2)P(OR)(2)}(2)] 6 (R= (i)Pr, 6A; Et, 6B), trinuclear [Cu(3)(mu-dppe)(3)(mu-Cl)(2){S(2)P(O(i)Pr)(2)}] 9, and polymeric [Cu(mu(2)-dppe){S(2)P(OR)(2)}](n) (R = Et, 7; (i)Pr, 8) complexes. The formation of 1 and 5 involved the abstraction of chloride from dichloromethane when the Cu/S(2)P(OR)(2) ratio exceeded 1, but when ratio was 1:1, no Cl abstraction occurred, as in compound 4. Compound 9, however, was obtained as a 12% byproduct in the synthesis of 8 using a 1:1:1 ratio of Cu/dppe/S(2)P(O(i)Pr)(2). The chloride binds to Cu atoms in a mu(3)-Cl mode by capping one face of the Cu(3) triangle of cluster 1. A mu(4)-Cl caps a single tetragonal face of the trigonal prism of cluster 5, and in the cluster 9, two chlorides bond in mu(2)-Cl modes. Both clusters 2 and 3 exhibit the mu(3)-S mode of bonding for dtp ligands. Only cluster 5 exhibited close Cu...Cu contacts (2.997-3.0238 A). All of compounds were characterized by single-crystal X-ray diffraction and pertinent crystallographic data for 1, 5, and 9 are are follows: (1) C(79)H(76)ClCu(3)F(6)O(2)P(8)S(2), triclinic, P, a = 11.213(1) A, b = 14.142(1) A, c = 25.910(2) A, alpha = 95.328(2) degrees , beta = 99.594(2) degrees , gamma = 102.581(2) degrees , V = 3918.2(6) A(3), Z = 2; (5) C(74)H(100)BClCu(6)F(4)O(8)P(8)S(8), monoclinic, P2(1)/n, a = 25.198(4) A, b = 15.990(3) A, c = 25.421(4) A, beta = 106.027(3) degrees , V = 9845(3)A(3), Z = 4; (9) C(84)H(86)Cl(2)Cu(3)O(2)P(7)S(2), monoclinic, C2/c, with a = 24.965(3) A, b = 17.058(2) A, c = 20.253(2) A, beta = 95.351(4) degrees , V = 8587.4(17)A(3), Z = 4.     

Exploring stereogenic phosphorus: synthetic strategies for diphosphines containing bulky,highly symmetric substituents

Diphosphine ligands bearing highly symmetric, bulky substituents at a stereogenic P atom were prepared, exploiting established protocols, which include the use of chiral synthons such as 3,4-dimethyl-2,5-diphenyl-1,3,2-oxazaphospholidine-2-borane (3a) and phenylmethylchlorophosphine borane (10) and the enantioselective deprotonation of dimethylarylphosphine boranes. However, only (Bu(t)())(Me)PCH(2)CH(2)P(Bu(t)Me (8a) could be prepared from 3a. The diphosphines (S,S)-1,2-bis(mesitylmethylphosphino)ethane, ((S,S)-8b) and (S,S)-1,2-bis(9-anthrylmethylphosphino)ethane ((S,S)-8c), which contain 2,6-disubstituted aryl P-substituents, were prepared by Evans' sparteine-assisted enantioselective deprotonation of P(Ar)(Me)(2)(BH(3)) (Ar = mesityl or 9-anthryl), but the enantioselectivity did not exceed 37% ee. The asymmetrically substituted, methylene-bridged diphosphine (2R,4R)-(Ph)(CH(3))PCH(2)P(Mes)(CH(3)) ((2R,4R)-12) (Mes = mesityl) was prepared by the newly developed stereospecific reaction of the enantiomerically pure chlorophosphine borane PCl(Ph)(Me)(BH(3)) (10) with the racemic, monolithiated dimethylmesitylphosphine borane P(Mes)(Me)(CH(2)Li)(BH(3)). Diastereomerically pure (2R,4R)-12 was obtained with 86% ee. The rhodium(I) derivatives [Rh(COD)(P-P)]BF(4) containing the diphosphine ligands 8a, 8b, and 12, as well as the previously reported (S,S)-1,2-bis(1-naphthylphenylphosphino)ethane ((S,S)-8d), were prepared and tested in the enantioselective catalytic hydrogenation of acetamidocinnamates. The best catalytic result (98.6% ee) was obtained with [Rh(COD)(8d)](+) as catalyst and methyl Z-alpha-acetamidocinnamate as substrate. Some of the catalytic results are discussed in terms of the preferred conformations of the substituents at phosphorus, as calculated by molecular modeling.     

Structural Aspects of Lithium Arenethiolate Complexes with Intramolecular Coordinating Amine Donors

Reaction of aryllithium reagents LiR (R = C(6)H(4)((R)-CH(Me)NMe(2))-2 (1a), C(6)H(3)(CH(2)NMe(2))(2)-2,6 (1b), C(6)H(4)(CH(2)N(Me)CH(2)CH(2)OMe)-2 (1c)) with 1 equiv of sulfur (1/8 S(8)) results in the quantitative formation of the corresponding lithium arenethiolates [Li{SC(6)H(4)((R)-CH(Me)NMe(2))-2}](6) (3), [Li{SC(6)H(3)(CH(2)NMe(2))(2)-2,6}](6) (4), and [Li{SC(6)H(4)(CH(2)N(Me)CH(2)CH(2)OMe)-2}](2) (5). Alternatively, 3 can be prepared by reacting the corresponding arenethiol HSC(6)H(4)((R)-CH(Me)NMe(2))-2 (2) with (n)BuLi. X-ray crystal structures of lithium arenethiolates 3 and 4, reported in abbreviated form, show them to have hexanuclear prismatic and hexanuclear planar structures, respectively, that are unprecedented in lithium thiolate chemistry. The lithium arenethiolate [Li{SC(6)H(4)(CH(2)N(Me)CH(2)CH(2)OMe)-2}](2) (5) is dimeric in the solid state and in solution, and crystals of 5 are monoclinic, space group P2(1)/c, with a = 17.7963(9) ?, b = 8.1281(7) ?, c = 17.1340(10) ?, beta = 108.288(5) degrees, Z = 4, and final R = 0.047 for 4051 reflections with F > 4sigma(F). Hexameric 4 reacts with 1 equiv of lithium iodide and 2 equiv of tetrahydrofuran to form the dinuclear adduct [Li(2)(SAr)(I)(THF)(2)] (6). Crystals of 6 are monoclinic, space group P2(1)/c, with a = 13.0346(10) ?, b = 11.523(3) ?, c = 16.127(3) ?, beta = 94.682(10) degrees, Z = 4, and final R = 0.059 for 3190 reflections with F > 4sigma(F).     

Facile allylic C-H bond activation on the bridging disulfide ligand in the Ru(III) dinuclear complex having a conjugated RuSSRu core

Treatment of [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)(mu-S(2))](CF(3)SO(3))(4) (1), which is prepared by the reaction of [[RuCl(P(OCH(3))(3))(2)](2)(mu-S(2))(mu-Cl)(2)] (2) with 4 equiv of AgCF(3)SO(3), with terminal alkenes such as 1-pentene, allyl ethyl ether, allyl phenyl ether, 1,4-hexadiene, and 3-methyl-1-butene, resulted in the formation of complexes carrying a C(3)S(2) five-membered ring, [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SCH(2)CH(2)CR(1)R(2)S]](CF(3)SO(3))(4) (3, R(1) = CH(2)CH(3), R(2) = H, 40%; 4, R(1) = OCH(2)CH(3), R(2) = H, 60%; 5, R(1) = OC(6)H(5), R(2) = H, 73%; 6, R(1) = CH=CHCH(3), R(2) = H, 48%; 7, R(1) = R(2) = CH(3), 40%). Reaction of 1 with methylenecycloalkanes was found to give several different types of products, depending on the ring size of the substrates. A trace of [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SCH(CH(2)CH(2))CH(CH(3))S]](CF(3)SO(3))(4) (9) having a C(2)S(2) four-membered ring to bridge the two Ru atoms was obtained by the reaction of 1 with methylenecyclobutane, whereas the reaction with methylenecyclohexane gave [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-S(CH(2)(C=CHCH(2)CH(2)CH(2)CH(2))S)](CF(3)SO(3))(3) (10) in 69% yield via C-S bond formation and elimination of a proton. Throughout these reactions with alkenes giving a variety of products, the activation of the allylic C-H bond is always the essential and initial key step.     

Syntheses, structures, and reactivity of new pentamethylcyclopentadienyl-rhodium(III) and -iridium(III) 4-acyl-5-pyrazolonate complexes

New [CpM(Q)Cl] complexes (M = Rh or Ir, Cp = pentamethylcyclopentadienyl, HQ = 1-phenyl-3-methyl-4R(C=O)-pyrazol-5-one in general, in detail HQ(Me), R = CH(3); HQ(Et), R = CH(2)CH(3); HQ(Piv), R = CH(2)-C(CH(3))(3); HQ(Bn), R = CH(2)-(C(6)H(5)); HQ(S), R = CH-(C(6)H(5))(2)) have been synthesized from the reaction of [CpMCl(2)](2) with the sodium salt, NaQ, of the appropriate HQ proligand. Crystal structure determinations for a representative selection of these [CpM(Q)Cl] compounds show a pseudo-octahedral metal environment with the Q ligand bonded in the O,O'-chelating form. In each case, two enantiomers (S(M)) and (R(M)) arise, differing only in the metal chirality. The reaction of [CpRh(Q(Bn))Cl] with MgCH(3)Br produces only halide exchange with the formation of [CpRh(Q(Bn))Br]. The [CpRh(Q)Cl] complexes react with PPh(3) in dichloromethane yielding the adducts CpRh(Q)Cl/PPh(3) (1:1) which exist in solution in two different isomeric forms. The interaction of [CpRh(Q(Me))Cl] with AgNO(3) in MeCN allows generation of [CpRh(Q(Me))(MeCN)]NO(3).3H(2)O, whereas the reaction of [CpRh(Q(Me))Cl] with AgClO(4) in the same solvent yields both [CpRh(Q(Me))(H(2)O)]ClO(4) and [CpRh(Cl)(H(2)O)(2)]ClO(4); the H(2)O molecules derive from the not-rigorously anhydrous solvents or silver salts.     

Low temperature kinetics, crossed beam dynamics and theoretical studies of the reaction S((1)D) + CH4 and low temperature kinetics of S((1)D) + C2H2

The reaction between sulfur atoms in the first electronically excited state, S((1)D), and methane (CH(4)), has been investigated in a complementary fashion in (a) crossed-beam dynamics experiments with mass spectrometric detection and time-of-flight (TOF) analysis at two collision energies (30.4 and 33.6 kJ mol(-1)), (b) low temperature kinetics experiments ranging from 298 K down to 23 K, and (c) electronic structure calculations of stationary points and product energetics on the CH(4)S singlet potential energy surface. The rate coefficients for total loss of S((1)D) are found to be very large (ca. 2 × 10(-10) cm(3) molec(-1) s(-1)) down to very low temperatures indicating that the overall reaction is barrier-less. Similar measurements are also performed for S((1)D) + C(2)H(2), and also for this system the rate coefficients are found to be very large (ca. 3 × 10(-10) cm(3) molec(-1) s(-1)) down to very low temperatures. From laboratory angular and TOF distributions at different product masses for the reaction S((1)D) + CH(4), it is found that the only open reaction channel at the investigated collision energies is that leading to SH + CH(3). The product angular, T(θ), and translational energy, P(E'(T)), distributions in the center-of-mass frame are derived. The reaction dynamics are discussed in terms of two different micromechanisms: a dominant long-lived complex mechanism at small and intermediate impact parameters with a strongly polarized T(θ), and a direct pickup-type (stripping) mechanism occurring at large impact parameters with a strongly forward peaked T(θ). Interpretation of the experimental results on the S((1)D) + CH(4) reaction kinetics and dynamics is assisted by high-level theoretical calculations on the CH(4)S singlet potential energy surface. The dynamics of the SH + CH(3) forming channel are compared with those of the corresponding channel (leading to OH + CH(3)) in the related O((1)D) + CH(4) reaction, previously investigated in crossed-beams in other laboratories at comparable collision energies. The possible astrophysical relevance of S((1)D) reactions with hydrocarbons, especially in the chemistry of cometary comae, is discussed.     

O-Methylephedrine: a versatile and highly efficient ortho-directing group. Synthesis of enantiopure 1,2-disubstituted ferrocene derivatives.

O-Methylephedrine was identified as a very efficient chiral auxiliary for ortho-lithiation reactions of ferrocenes. (1R,2S)-O-Methylephedrine [CH(3)NHCH(CH(3))CH(Ph)OCH(3)] was reacted with N-ferrocenylmethyl-N,N,N-trimethylammonium iodide [FcCH(2)N(CH(3))(3)I; Fc = ferrocenyl] to give (1R,2S)-N-ferrocenylmethyl-O-methylephedrine. Treatment of this compound with t-BuLi in pentane followed by quenching with the electrophiles iodine, dibromotetrafluoroethane, chlorodiphenylphosphine or benzophenone gave 2-substituted ferrocenes in 98% de and with the (R(p))-ferrocene configuration. Subsequently, the chiral auxiliary could be replaced by systems including dimethylamine, acetate, diaryl- or dialkylphosphines to give a number of enantiopure bifunctional 1,2-disubstituted ferrocene derivatives such as (R(p))-N-2-iodo- or (R(p))-N-2-bromoferrocenylmethyldimethylamine or (R(p))-2-acetoxymethyl-1-diphenylphosphinoferrocene. As an application, ferrocenyl diphosphines possessing a planar (R(p))-ferrocene configuration only [1,2-(PPh(2))FcCH(2)PR(2), R = Cy, Ph, [3,5-(CF(3))(2)Ph]] were synthesized in three steps from O-methylephedrine and N-ferrocenylmethyl-N,N,N-trimethylammonium iodide in up to 77% overall yield.     

Synthesis, helicity, and chromism of optically active poly(phenylacetylene)s carrying different amino acid moieties and pendant terminal groups

Functional phenylacetylene derivatives containing l-alanine and l-leucine moieties with chiral menthyl and achiral n-octyl terminal groups {HC[triple bond]C-C6H4-p-CONHCH(R)CO2R': R = CH3, R'= (-)-(1R,2S,5R)-menthyl [1(-)]; R = CH2CH(CH2)3, R' = (-)-(1R,2S,5R)-menthyl [2(-)]; R'= CH2CH(CH2)3, R' = (+)-(1S,2R,5S)-menthyl [2(+)]; R'= CH2CH(CH2)3, R' = (CH2)7CH3 (2o)} are synthesized. Polymerizations of the acetylene monomers are effected by organorhodium catalysts, giving corresponding polymers P1(-), P2(-), P2(+), and P2o of high molecular weights (Mw up to 1.2 x 10(6)) in high yields (up to 89%). The polymers are thermally stable (Td >or= 300 degrees C) and soluble in common organic solvents. The polymer structures are characterized by IR, NMR, UV, and CD spectroscopies. Intense CD signals are observed in the visible spectral region, indicating that the polymer chains are taking a helical conformation with an excess of preferred handedness. The backbone conjugation and chain helicity of the polymers can be tuned by changing their molecular structures [(a)chiral pendant groups] and by applying external stimuli (solvent and pH). Addition of trifluoroacetic acid to the polymer solutions decreases their molar ellipticities and enhances their backbone conjugations, inducing a halochromism with a continuous and reversible color change (yellow <==> red).     

The subtle electronic effects of alkyl groups on the conformational equilibria and intramolecular hydrogen-bond strength in cis-3-alkoxycyclohexanols

(1)H NMR data for cis-3-n-propoxycyclohexanol (cis-3-PCH) and cis-3-isopropoxy-cyclohexanol (cis-3-ICH) show that a concentration increase shifts the conformational equilibrium from the diaxial (aa) conformer, stabilized by an intramolecular hydrogen bond (IAHB), to the diequatorial (ee) conformer [X(ee)=42% and 21% (at 0.01molL(-1)) to 58% and 56% (at 0.40molL(-1)), in CCl(4,) respectively] due to intermolecular hydrogen bonds (IEHB), as confirmed by IR data. The Deltanu values, obtained by IR spectra, indicated that increasing the size of the OR group [R=CH(3), CH(2)CH(2)CH(3) and CH(CH(3))(2)], increases the IAHB strength, due to an increase in the inductive effect of R group, which makes the oxygen lone pairs more available for an IAHB with OH group, in opposition to the steric effect. The percentage of ee conformer increases with the solvent basicity for cis-3-PCH and cis-3-ICH, from 48% and 36% in CCl(4) to 97% and 96% in DMSO, respectively. Values of 4.58, 6.06 and 6.33kcalmol(-1) for the IAHB strength in cis-3-PCH, cis-3-ICH and cis-3-TCH (cis-3-tert-butoxycyclohexanol), respectively, were obtained, from the theoretical data through the CBS-4M method, confirming the experimental results and indicating that the IAHB strength increases with the increasing bulk of OR substituent in this series of compounds.     

Tin(II) amide/alkoxide coordination compounds for production of Sn-based nanowires for lithium ion battery anode materials

A series of tin(II) amide alkoxides ([(OR)Sn(NMe(2))](n)) and tin(II) alkoxides ([Sn(OR)(2)](n)) were investigated as precursors for the production of tin oxide (SnO(x)) nanowires. The precursors were synthesized from the metathesis of tin dimethylamide ([Sn(NMe(2))(2)](2)) and a series of aryl alcohols {H-OAr = H-OC(6)H(4)(R)-2: R = CH(3) (H-oMP), CH(CH(3))(2) (H-oPP), C(CH(3))(3) (H-oBP)] or [H-OC(6)H(3)(R)(2)-2,6: R = CH(3) (H-DMP), CH(CH(3))(2) (H-DIP), C(CH(3))(3) (H-DBP)]}. The 1:1 products were all identified as the dinuclear species [(OAr)Sn(μ-NMe(2))](2) where OAr = oMP (1), oPP (2), oBP (3), DMP (4), DIP (5), DBP (6). The 1:2 products were identified as either a polymer ([Sn(μ-OAr)(2)](∞) (where OAr = oMP (7), oPP (8)), dinuclear [(OAr)Sn(μ-OAr)](2) (where OAr = oBP (9), DMP (10) or DIP/HNMe(2) (11)), or mononuclear [Sn(DBP)(2)] (12) complexes. These novel families of compounds (heteroleptic 1-6, and homoleptic 7-12) were evaluated for the production of SnO(x) nanowires using solution precipitation (SPPT; oleylamine/octadecene solvent system) or electrospinning (ES; THF solvent) processing conditions. The SPPT route that employed the heteroleptic precursors yielded mixed phases of Sn(o):romarchite [1 (100:0); 2 (80:20); 3 (68:32); 4 (86:14); 5 (66:35); 6 (88:12)], with a variety of spherical sized particles [1 (350-900 nm); 2 (150-1200 nm); 3 (250-950 nm); 4 (20-180 nm); 5 (80-400 nm); 6 (40-200 nm)]. For the homoleptic precursors, similar phased [7 (80:20); 8 (23:77); 9 (15:85); 10 (34:66); 11 (77:23); 12 (77:23)] spherical nanodots were isolated [7 (50-300 nm); 8: (irregular); 10 (200-800 nm); 11 (50-150 nm); 12 (50-450 nm)], except for 9 which formed polycrystalline rods [Sn(o):romarchite (15:85)] with aspect ratios >100. From ES routes, the heteroleptic species were found to form 'tadpole-shaped' materials whereas the homoleptic species formed electrosprayed nanodots. The one exception noted was for 7, where, without use of a polymer matrix, nanowires of Sn(o), decorated with micron sized 'balls' were observed. Due to the small amount of material generated, PXRD patterns were inconclusive to the identity of the generated material; however, cyclic voltammetry on select samples was used to tentatively identify the final Sn(o) (from 7) with the other sample identified as SnO(x) (from 1).     

Synthesis, structure, and reactivity of fluorous phosphorus/carbon/phosphorus pincer ligands and metal complexes

Reactions of the diphosphine 1,3-C6H4(CH2PH2)2 and fluorous alkenes H2C=CHR(fn)(R(fn)=(CF2)(n-1)CF3; n = 6, 8) at 75 degrees C in the presence of AIBN give the title ligands 1,3-C6H4(CH2P(CH2CH2R(fn))2)2(3-R(fn)) and byproducts 1,3-C6H4(CH3)(CH2P(CH2CH2R(fn))2)(4-R(fn)) in 1 : 3 to 1 : 5 ratios. Workups give -R(fn) in 4--17% yields. Similar results are obtained photochemically. Reaction of 1,3-C6H4(CH2Br)2 and HP(CH2CH2R(f8))2 (5) at 80 degrees C (neat, 1 : 2 mol ratio) gives instead of simple substitution the metacyclophane [1,3-C6H4(CH2P(CH2CH2R(f8))2 CH2-1,3-C(6)H(4)CH(2)P[lower bond 1 end](CH2CH2R(f8))2C[upper bond 1 end]H2](2+)2Br-, which upon treatment with LiAlH(4) yields 3-R(f8)(20%), 4-R(f8), and other products. Efforts to better access 3-R(f8), either by altering stoichiometry or using various combinations of the phosphine borane (H3B)PH(CH2CH2R(f8))2 and base, are unsuccessful. Reactions of 3-R(fn) with Pd(O2CCF3)2 and [IrCl(COE)2]2(COE=cyclooctene) give the palladium and iridium pincer complexes (2,6,1-C6H3(CH2 P(CH2CH2R(fn))(2)(2)Pd(O2CCF3)(10-R(fn); 80-90%) and (2,6,1-C6H3(CH2P(CH2CH2R(f8))2)2)Ir(Cl)(H)(11-R(f8); 29%), which exhibit CF3C6F(11)/toluene partition coefficients of >96 : <4. The crystal structure of 10-R(f8) shows CH2CH2R(f8) groups with all-anti conformations that extend in parallel above and below the palladium square plane to create fluorous lattice domains. NMR monitoring shows a precursor to 11-R(f8) that is believed to be a COE adduct.     

Ruthenium complexes with chiral tetradentate imino-sulfoxide ligands

Treatment of 2-(methylsulfinyl)benzaldehyde (1) with ethylenediamine or (1R,2R)-(-)-1,2-diaminocyclohexane afforded N,N'-bis[2-(methylsulfinyl)benzylidene]ethylenediamine (L(1)) or (1R,2R)-N,N'-bis[2-(methylsulfinyl)benzylidene]-1,2-cyclohexanedia mine (L(2)), respectively. Lithiation of 2-bromobenzaldehyde diethylacetal with n-BuLi/TMEDA followed by reaction with (1R,2S,5R)-(-)-menthyl-(S)-p-toluenesulfinate afforded 2-(S)-(p-tolylsulfinyl)benzaldehyde diethyl acetal (2). Deprotection of 2 with pyridinium tosylate followed by condensation with ethylenediamine, (1R,2R)-(-)-diaminocyclohexane, or (S,S)-(+)-diaminocyclohexane afforded N,N'-bis[2-(S)-(p-tolylsulfinyl)benzylidene]ethylenediamine (L(3)), (1R,2R)-N,N'-bis[2-(S)-(p-tolylsulfinyl)benzylidene]-1,2-cyclohexanediamine ((R,R)-L(4)), or (S,S)-N,N'-bis[2-(S)-(p-tolylsulfinyl)benzylidene]-1,2-cyclohexanediamine ((S,S)-L(4)), respectively. Treatment of [Ru(PPh(3))(3)Cl(2)] with L afforded trans-[Ru(L)Cl(2)] [L = L(1) (3), L(2) (4), L(3) (5), (R,R)-L(4) ((R,R)-6), (S,S)-L(4) ((S,S)-6)]. The X-ray structures of (S(S),R(S))-4, (R,R)-6, and (S,S)-6 have been determined. The average Ru-N, Ru-S, and Ru-Cl distances in (S(S),R(S))-4 are 2.063, 2.2301, and 2.4039 A, respectively. The corresponding distances in (R,R)-6 are 2.071, 2.256, and 2.411 A, and those in (S,S)-6, 2.058, 2.2275, and 2.3831 A. Compound 3 exhibited a reversible Ru(III/II) couple at 0.56 V vs Cp(2)Fe(+/0) in CH(2)Cl(2). Treatment of 3 with AgNO(3) in water afforded the aqua compound trans-[Ru(L(1))Cl(H(2)O)][PF(6)] (7), which has been characterized by X-ray crystallography. The Ru-Cl, Ru-O, average Ru-N, and average Ru-S distances in 7 are 2.3733(6), 2.1469(16), 2.071, and 2.2442 A, respectively. Treatment of 3 with AgNO(3) followed by reaction with PPh(3) afforded [Ru(L(1))(PPh(3))(2)][PF(6)](2) (8). Treatment of [Os(PPh(3))(3)Cl(2)] with L(1) resulted in deoxygenation of one sulfoxide group of L(1) and formation of [Os(L(5))Cl(2)(PPh(3))] (9) (L(5) = N-[2-(methylsulfinyl)benzylidene]-N'-[2-(methylthio)benzylididene]ethylenediamine), which has been characterized by X-ray crystallography. The average Os-S(O), Os-N(trans to P), Os-N(trans to S), Os-P, and Os-Cl distances are 2.1931, 2.085, 2.175, 2.3641, and 2.4266 A, respectively.     

New palladium-catalyzed cross-coupling routes to carbon functionalized metallatricarbadecaboranes

A general method for the synthesis of cage-carbon-functionalized cyclopentadienyl iron and cyclopentadienyl ruthenium tricarbadecaboranyl complexes has been developed that employs palladium-catalyzed Sonogashira, Heck, and Stille cross-coupling reactions directed at a cage-carbon haloaryl substituent. The key Li(+)[6-(p-XC(6)H(4))-nido-5,6,9-C(3)B(7)H(9)(-)] (X = I (1), Br (2), Cl (3)) haloaryl-tricarbadecaboranyl anionic ligands were synthesized in high yields via the reaction of the arachno-4,6-C(2)B(7)H(12)(-) anion with the corresponding p-halobenzonitriles (p-XC(6)H(4)-CN). The reactions of the salts 1-3 with (η(5)-C(5)H(5))Fe(CO)(2)I and (η(5)-C(5)H(5))Ru(CH(3)CN)(3)PF(6) were then used to produce the haloaryl complexes 1-(η(5)-C(5)H(5))-2-(p-XC(6)H(4))-closo-1,2,3,4-MC(3)B(7)H(9) (M = Fe, X = I (4), Br (5), Cl (6) and M = Ru, X = I (7), Br (8), Cl (9)). The sonication-promoted Sonogashira coupling reactions of 4 with terminal alkynes catalyzed by Pd(dppf)(2)Cl(2)/CuI yielded the alkynyl-linked derivatives 1-(η(5)-C(5)H(5))-2-p-RC(6)H(4)-closo-1,2,3,4-FeC(3)B(7)H(9) (R = (PhC≡C)- (10), (CH(3)CH(2)C(O)OCH(2)C≡C)- (11), ((η(5)-C(5)H(5))Fe(η(5)-C(5)H(4)C≡C))- (12)). Heck reactions of 4 with terminal alkenes catalyzed by Pd(OAc)(2) yielded the alkene-functionalized products 1-(η(5)-C(5)H(5))-2-p-RC(6)H(4)-closo-1,2,3,4-FeC(3)B(7)H(9) (R = (PhCH(2)CH═CH)- (13), (CH(3)(CH(2))(2)CH═CH)- (14)), while the Stille cross-coupling reactions of 4 with organotin compounds catalyzed by Pd(PPh(3))(2)Cl(2) afforded the complexes 1-(η(5)-C(5)H(5))-2-p-RC(6)H(4)-closo-1,2,3,4-FeC(3)B(7)H(9) (R = Ph- (15), (CH(2)═CH)- (16), (CH(2)═CHCH(2))- (17)). These reactions thus provide facile and systematic access to a wide variety of new types of functionalized metallatricarbadecaboranyl complexes with substituents needed for potential metallocene-like biomedical and/or optoelectronic applications.     

Dehydration reaction of hydroxyl substituted alkenes and alkynes on the Ru(2)S(2) complex

A variety of inter- and intramolecular dehydration was found in the reactions of [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)(mu-S(2))](CF(3)SO(3))(4) (1) with hydroxyl substituted alkenes and alkynes. Treatment of 1 with allyl alcohol gave a C(3)S(2) five-membered ring complex, [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SCH(2)CH(2)CH(OCH(2)CH=CH(2))S]](CF(3)SO(3))(4) (2), via C-S bond formation after C-H bond activation and intermolecular dehydration. On the other hand, intramolecular dehydration was observed in the reaction of 1 with 3-buten-1-ol giving a C(4)S(2) six-membered ring complex, [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2) [mu-SCH(2)CH=CHCH(2)S]](CF(3)SO(3))(4) (3). Complex 1 reacts with 2-propyn-1-ol or 2-butyn-1-ol to give homocoupling products, [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SCR=CHCH(OCH(2)C triple bond CR)S]](CF(3)SO(3))(4) (4: R = H, 5: R = CH(3)), via intermolecular dehydration. In the reaction with 2-propyn-1-ol, the intermediate complex having a hydroxyl group, [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SCH=CHCH(OH)S]](CF(3)SO(3))(4) (6), was isolated, which further reacted with 2-propyn-1-ol and 2-butyn-1-ol to give 4 and a cross-coupling product, [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SCH=CHCH(OCH(2)C triple bond CCH(3))S]](CF(3)SO(3))(4) (7), respectively. The reaction of 1 with diols, (HO)CHRC triple bond CCHR(OH), gave furyl complexes, [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SSC=CROCR=CH]](CF(3)SO(3))(3) (8: R = H, 9: R = CH(3)) via intramolecular elimination of a H(2)O molecule and a H(+). Even though (HO)(H(3)C)(2)CC triple bond CC(CH(3))(2)(OH) does not have any propargylic C-H bond, it also reacts with 1 to give [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SCH(2)C(=CH(2))C(=C=C(CH(3))(2))]S](CF(3)SO(3))(4) (10). In addition, the reaction of 1 with (CH(3)O)(H(3)C)(2)CC triple bond CC(CH(3))(2)(OCH(3)) gives [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(2)][mu-S=C(C(CH(3))(2)OCH(3))C=CC(CH(3))CH(2)S][Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)]](CF(3)SO(3))(4) (11), in which one molecule of CH(3)OH is eliminated, and the S-S bond is cleaved.     

3,3'-Bis(trisarylsilyl)-substituted binaphtholate rare earth metal catalysts for asymmetric hydroamination

Chiral 3,3'-bis(trisarylsilyl)-substituted binaphtholate rare earth metal complexes (R)-[Ln{Binol-SiAr3}(o-C6H4CH2NMe2)(Me2NCH2Ph)] (Ln = Sc, Lu, Y; Binol-SiAr3 = 3,3'-bis(trisarylsilyl)-2,2'-dihydroxy-1,1'-binaphthyl; Ar = Ph (2-Ln), 3,5-xylyl (3-Ln)) and (R)-[La{Binol-Si(3,5-xylyl)3}{E(SiMe3)2}(THF)2] (E = CH (4a), N (4b)) are accessible via facile arene, alkane, and amine elimination. They are efficient catalysts for the asymmetric hydroamination/cyclization of aminoalkenes, giving TOF of up to 840 h(-1) at 25 degrees C for 2,2-diphenyl-pent-4-enylamine (5c) using (R)-2-Y. Enantioselectivities of up to 95% ee were achieved in the cyclization of 5c with (R)-2-Sc. The reactions show apparently zero-order rate dependence on substrate concentration and first-order rate dependence on catalyst concentration, but rates depend on total amine concentrations. Activation parameters for the cyclization of pent-4-enylamine using (R)-2-Y (deltaH(S)(double dagger) = 57.4(0.8) kJ mol(-1) and deltaS(S)(double dagger) = -102(3) J K(-1) mol(-1); deltaH(R)(double dagger) = 61.5(0.7) kJ mol(-1) and deltaS(R)(double dagger) = -103(3) J K(-1) mol(-1)) indicate a highly organized transition state. The binaphtholate catalysts were also applied to the kinetic resolution of chiral alpha-substituted aminoalkenes with resolution factors f of up to 19. The 2,5-disubstituted aminopentenes were formed in 7:1 to > or = 50:1 trans diastereoselectivity, depending on the size of the alpha-substituent of the aminoalkene. Rate studies with (S)-1-phenyl-pent-4-enylamine ((S)-15e) gave the activation parameters for the matching (deltaH(double dagger) = 52.2(2.8) kJ mol(-1), deltaS(double dagger) = -127(8) J K(-1) mol(-1) using (S)-2-Y) and mismatching (deltaH(double dagger) = 57.7(1.3) kJ mol(-1), deltaS(double dagger) = -126(4) J K(-1) mol(-1) using (R)-2-Y) substrate/catalyst combination. The absolute configuration of the Mosher amide of (2S)-2-methyl-4,4-diphenyl-pyrrolidine and (2R)-methyl-(5S)-phenyl-pyrrolidinium chloride, prepared from (S)-15e, were determined by crystallographic analysis. Catalyst (R)-4a showed activity in the anti-Markovnikov addition of n-propylamine to styrene.     

A computational study of the lowest singlet and triplet states of neutral and dianionic 1,2-substituted icosahedral and octahedral o-carboranes

This work introduces a calibrated B3LYP/6-31G(d) study on the electronic structure of singlet and triplet neutral species of 1,2-substituted icosahedral 1,2-R(2)-1,2-C(2)B(10)H(10) and octahedral 1,2-R(2)-1,2-C(2)B(4)H(4) molecules with R = {H, OH, SH, NH(2), PH(2), CH(3), SiH(3)} and their respective dianions formed by proton removal on each R group. A variety of small adiabatic singlet-triplet gaps DeltaE(ST) are obtained from these systems ranging from 2.93 eV (R = NH(2)) 相似文献