How large is the static electric (hyper)polarizability anisotropy in HXeI?

An extensive conventional ab initio and density functional theory investigation reveals that HXeI is a polar molecule with large multipole moments and highly anisotropic (hyper)polarizability. At the CCSD(T) level of theory our best values for the mean (hyper)polarizability are alphae(2)a(0) (2)E(h) (-1)=101.46, betae(3)a(0) (3)E(h) (-2)=-850.7, and gammae(4)a(0) (4)E(h) (-3)=18.7x10(3). The corresponding anisotropies are Deltaalphae(2)a(0) (2)E(h) (-1)=119.66, Deltabetae(3)a(0) (3)E(h) (-2)=-2518.7, Delta(1)gammae(4)a(0) (4)E(h) (-3)=-249.1x10(3), and Delta(2)gammae(4)a(0) (4)E(h) (-3)=-99.6x10(3). The longitudinal components of the (hyper)polarizability are dominant. Our value for the anisotropy of the dipole polarizability is considerably larger than the recent empirical estimate of 22.9 e(2)a(0) (2)E(h) (-1) [N. H. Nahler et al., J. Chem. Phys. 119, 224 (2003)]. The results of the insertion of Xe into HI are quantified by the calculation of the differential (hyper)polarizability at the MP2 level of theory: alpha(diff) identical withalpha(HXeI)-alpha(HI)-alpha(Xe)=36.29 e(2)a(0) (2)E(h) (-1) and gamma(diff) identical with gamma(HXeI)-gamma(HI)-gamma(Xe)=18.1x10(3) e(4)a(0) (4)E(h) (-3).     

Deviation between the chemistry of Ce(IV) and Pu(IV) and routes to ordered and disordered heterobimetallic 4f/5f and 5f/5f phosphonates

The heterobimetallic actinide compound UO(2)Ce(H(2)O)[C(6)H(4)(PO(3)H)(2)](2)·H(2)O was prepared via the hydrothermal reaction of U(VI) and Ce(IV) in the presence of 1,2-phenylenediphosphonic acid. We demonstrate that this is a kinetic product that is not stable with respect to decomposition to the monometallic compounds. Similar reactions have been explored with U(VI) and Ce(III), resulting in the oxidation of Ce(III) to Ce(IV) and the formation of the Ce(IV) phosphonate, Ce[C(6)H(4)(PO(3)H)(PO(3)H(2))][C(6)H(4)(PO(3)H)(PO(3))]·2H(2)O, UO(2)Ce(H(2)O)[C(6)H(4)(PO(3)H)(2)](2)·H(2)O, and UO(2)[C(6)H(4)(PO(3)H)(2)](H(2)O)·H(2)O. In comparison, the reaction of U(VI) with Np(VI) only yields Np[C(6)H(4)(PO(3)H)(2)](2)·2H(2)O and aqueous U(VI), whereas the reaction of U(VI) with Pu(VI) yields the disordered U(VI)/Pu(VI) compound, (U(0.9)Pu(0.1))O(2)[C(6)H(4)(PO(3)H)(2)](H(2)O)·H(2)O, and the Pu(IV) phosphonate, Pu[C(6)H(4)(PO(3)H)(PO(3)H(2))][C(6)H(4)(PO(3)H)(PO(3))]·2H(2)O. The reactions of Ce(IV) with Np(VI) yield disordered heterobimetallic phosphonates with both M[C(6)H(4)(PO(3)H)(PO(3)H(2))][C(6)H(4)(PO(3)H)(PO(3))]·2H(2)O (M = Ce, Np) and M[C(6)H(4)(PO(3)H)(2)](2)·2H(2)O (M = Ce, Np) structures, as well as the Ce(IV) phosphonate Ce[C(6)H(4)(PO(3)H)(PO(3)H(2))][C(6)H(4)(PO(3)H)(PO(3))]·2H(2)O. Ce(IV) reacts with Pu(IV) to yield the Pu(VI) compound, PuO(2)[C(6)H(4)(PO(3)H)(2)](H(2)O)·3H(2)O, and a disordered heterobimetallic Pu(IV)/Ce(IV) compound with the M[C(6)H(4)(PO(3)H)(PO(3)H(2))][C(6)H(4)(PO(3)H)(PO(3))]·2H(2)O (M = Ce, Pu) structure. Mixtures of Np(VI) and Pu(VI) yield disordered heterobimetallic Np(IV)/Pu(IV) phosphonates with both the An[C(6)H(4)(PO(3)H)(PO(3)H(2))][C(6)H(4)(PO(3)H)(PO(3))]·2H(2)O (M = Np, Pu) and An[C(6)H(4)(PO(3)H)(2)](2)·2H(2)O (M = Np, Pu) formulas.     

Ni, Pd, Pt, and Ru complexes of phosphine-borate ligands

The species Cy(2)PHC(6)F(4)BF(C(6)F(5))(2) reacts with Pt(PPh(3))(4) to yield the new product cis-(PPh(3))(2)PtH(Cy(2)PC(6)F(4)BF(C(6)F(5))(2)) 1 via oxidative addition of the P-H bond of the phosphonium borate to Pt(0). The corresponding reaction with Pd(PPh(3))(4) affords the Pd analogue of 1, namely, cis-(PPh(3))(2)PdH(Cy(2)PC(6)F(4)BF(C(6)F(5))(2)) 3; while modification of the phosphonium borate gave the salt [(PPh(3))(3)PtH][(tBu(2)PC(6)F(4)BF(C(6)F(5))(2))] 2. Alternatively initial deprotonation of the phosphonium borate gave [tBu(3)PH][Cy(2)PC(6)F(4)BF(C(6)F(5))(2)] 4, [SIMesH][Cy(2)PC(6)F(4)BF(C(6)F(5))(2)] 5 which reacted with NiCl(2)(DME) yielding [BaseH](2)[trans-Cl(2)Ni(Cy(2)PC(6)F(4)BF(C(6)F(5))(2))(2)] (Base = tBu(3)P 6, SIMes 7) or with PdCl(2)(PhCN)(2) to give [BaseH](2)[trans-Cl(2)Pd(Cy(2)PC(6)F(4)BF(C(6)F(5))(2))(2)] (Base = tBu(3)P 8, SIMes 9). While [C(10)H(6)N(2)(Me)(4)H][tBu(2)PC(6)F(4)BF(C(6)F(5))(2)] 10 was also prepared. A third strategy for formation of a metal complex of anionic phosphine-borate derivatives was demonstrated in the reaction of (COD)PtMe(2) with the neutral phosphine-borane Mes(2)PC(6)F(4)B(C(6)F(5))(2) affording (COD)PtMe(Mes(2)PC(6)F(4)BMe(C(6)F(5))(2)) 11. Extension of this reactivity to tBu(2)PH(CH(2))(4)OB(C(6)F(5))(3)) was demonstrated in the reaction with Pt(PPh(3))(4) which yielded cis-(PPh(3))(2)PtH(tBu(2)P(CH(2))(4)OB(C(6)F(5))(3)) 12, while the reaction of [SIMesH][tBu(2)P(CH(2))(4)OB(C(6)F(5))(3)] 13 with NiCl(2)(DME) and PdCl(2)(PhCN)(2) afforded the complexes [SIMesH](2)[trans-Cl(2)Ni(tBu(2)PC(4)H(8)OB(C(6)F(5))(3))(2)] 14 and [SIMesH](2)[trans-PdCl(2)(tBu(2)P(CH(2))(4)OB(C(6)F(5))(3))(2)] 15, respectively, analogous to those prepared with 4 and 5. Finally, the reaction of 7 and 13with [(p-cymene)RuCl(2)](2) proceeds to give the new orange products [SIMesH][(p-cymene)RuCl(2)(Cy(2)PC(6)F(4)BF(C(6)F(5))(2))] 16 and [SIMesH][(p-cymene)RuCl(2)(tBu(2)P(CH(2))(4)OB(C(6)F(5))(3))] 17, respectively. Crystal structures of 1, 6, 10, 11, 12, and 16 are reported.     

Iodination of triazenide-bridged rhodium and iridium complexes: oxidative addition vs. one-electron oxidation

The triazenide-bridged tetracarbonyls [(OC)(2)Rh(mu-p-MeC(6)H(4)NNNC(6)H(4)Me-p)(2)M(CO)(2)] (M = Rh or Ir) undergo oxidative addition of iodine across the dimetal centre, giving the [RhM](4+) complexes [I(OC)(2)Rh(mu-p-MeC(6)H(4)NNNC(6)H(4)Me-p)(2)M(CO)(2)I], structurally characterised for M = Ir. The anionic tricarbonyl iodide [I(OC)Rh(mu-p-MeC(6)H(4)NNNC(6)H(4)Me-p)(2)Rh(CO)(2)](-) forms [I(2)(OC)Rh(mu-p-MeC(6)H(4)NNNC(6)H(4)Me-p)(2)Rh(CO)I](-) by initial one-electron transfer whereas the analogous tricarbonyl phosphine complexes [(OC)(Ph(3)P)Rh(mu-p-MeC(6)H(4)NNNC(6)H(4)Me-p)(2)M(CO)(2)] (M = Rh or Ir) undergo bridge cleavage, giving mononuclear [Rh(p-MeC(6)H(4)NNNC(6)H(4)Me-p)I(2)(CO)(PPh(3))] and dimeric [I(OC){RNNN(R)C(O)}M(mu-I)(2)M{C(O)N(R)NNR}(CO)I] (M = Rh or Ir, R = C(6)H(4)Me-p) in which CO has been inserted into a metal-nitrogen bond.     

Synthesis, characterization, and crystal structures of novel intramolecularly base-stabilized borane derivatives with six- and seven-membered chelate rings

The reaction of (2-dimethylaminophenyl)alcohols 1-HOX-2-NMe(2)C(6)H(4) [X = CPh(2) (1), X = CCy(2) (2), X = CPh(2)CH(2) (4)] and 1-phenylaminoalkyl-2-dimethylaminobenzene 1-HN(Ph)X-2-NMe(2)C(6)H(4) [X = C(H)Ph (3), C(H)PhCH(2) (5)] with BH(3)(THF) yielded the BH(2) derivatives 1-H(2)BOX-2-NMe(2)C(6)H(4) [X = CPh(2) (6), CCy(2) (7), CPh(2)CH(2) (9)] and 1-H(2)BN(Ph)X-2-NMe(2)C(6)H(4) [X = C(H)Ph (8), C(H)PhCH(2) (10)]. Treatment of 1-H(2)BOCPh(2)-2-NMe(2)C(6)H(4) (6) with acetic acid gave 1-(CH(3)COO)HBOCPh(2)-2-NMe(2)C(6)H(4) (11). Compounds 6-11 were characterized spectroscopically (NMR, IR, MS). Crystal structure determinations were carried out on 6-11, which are novel examples of structurally characterized BH(2) derivatives containing six- or seven-membered chelate rings. For the chiral compounds 8, 10, and 11, both enantiomers are present in the unit cell.     

Reaction of m-terphenyldichlorophosphanes with sodium azide: synthesis and characterization of stable azidocyclophosphazenes

Reaction of the m-terphenyldichlorophosphanes 2,6-(2-MeC(6)H(4))(2)C(6)H(3)PCl(2) (1), 2,6-(4-t-BuC(6)H(4))(2)C(6)H(3)PCl(2) (2), or 2,6-Mes(2)C(6)H(3)PCl(2) (3) with excess NaN(3) in acetonitrile at room temperature afforded the corresponding bisazidophosphanes 2,6-(2-MeC(6)H(4))(2)C(6)H(3)P(N(3))(2), 2,6-(4-t-BuC(6)H(4))(2)C(6)H(3)P(N(3))(2) (5), or 2,6-Mes(2)C(6)H(3)P(N(3))(2) (6) (Mes = 2,4,6-Me(3)C(6)H(2)), respectively. These compounds are thermally labile and decompose into a number of azidophosphazenes. The azidocyclophosphazenes [NP(N(3))(C(6)H(3)(4-t-BuC(6)H(4))(2)-2,6)](3) (4) and [NP(N(3))C(6)H(3)Mes(2)-2,6](2) (8) have been isolated from these mixtures. All compounds were characterized by (1)H, (13)C, (31)P NMR and IR spectroscopy. Crystal structures of 2, 4, and 8 were determined.     

Kinetic and donor stabilization of organotellurenyl iodides and azides

The first tellurium compounds containing the extremely bulky tris(phenyldimethylsilyl)methyl (Tpsi) and 2,6-bis(2,4,6-triisopropylphenyl)phenyl (2,6-Trip(2)C(6)H(3)) moieties have been synthesized and isolated. Careful oxidation of the tellurolate TpsiTeLi (1) resulted in the formation of the crowded ditellane (TpsiTe)(2) (2), and iodination of 2 gave the alkanetellurenyl iodide TpsiTeI (3). In a similar fashion, the terphenyl-substituted ditellane (2,6-Trip(2)C(6)H(3)Te)(2) (9) and the arenetellurenyl iodide 2,6-Trip(2)C(6)H(3)TeI (10) were prepared. Reaction of the iodides TpsiTeI (3) and 2,6-Trip(2)C(6)H(3)TeI (10), as well as TripTeI, MesTeI (Trip = 2,4,6-triisopropylphenyl, Mes = 2,4,6-tri-tert-butylphenyl), and the donor-stabilized 2-Me(2)NCH(2)C(6)H(4)TeI, with AgN(3) resulted in the formation and isolation of the corresponding tellurenyl azides TpsiTeN(3) (4), TripTeN(3) (7), MesTeN(3) (8), 2,6-Trip(2)C(6)H(3)TeN(3) (11), and 2-Me(2)NCH(2)C(6)H(4)TeN(3) (12). Furthermore, the corresponding tris(ethyldimethylsilyl)methyl-containing (Tesi) tellurium compounds (TesiTe)(2), TesiTeI (5), and TesiTeN(3) (6) have been prepared but could not be isolated in pure form. The crystal structures of TpsiTeLi (1), (TpsiTe)(2) (2), TpsiTeN(3) (4), 2,6-Trip(2)C(6)H(3)TeI (10), 2,6-Trip(2)C(6)H(3)TeN(3) (11), and 2-Me(2)NCH(2)C(6)H(4)TeN(3) (12) have been determined by X-ray diffraction. Additionally, computational studies of the molecules for which experimental structural data were available were performed.     

New titanium complexes with symmetric or asymmetric cis-9,10-dihydrophenanthrenediamide ligands formed through sequential intramolecular C-C bond-forming reactions

A series of new titanium(IV) complexes with symmetric or asymmetric cis-9,10-dihydrophenanthrenediamide ligands, cis-9,10-PhenH(2)(NR)(2)Ti(O(i)Pr)(2) [PhenH(2) = 9,10-dihydrophenanthrene, R = 2,6-(i)Pr(2)C(6)H(3) (2a), 2,6-Et(2)C(6)H(3) (2b), 2,6-Me(2)C(6)H(3) (2c)], cis-9,10-PhenH(2)(NR(1))(NR(2))Ti(O(i)Pr)(2) [R(1) = 2,6-(i)Pr(2)C(6)H(3), R(2) = 2,6-Et(2)C(6)H(3) (2d); R(1) = 2,6-(i)Pr(2)C(6)H(3), R(2) = 2,6-Me(2)C(6)H(3) (2e)], and [cis-9,10-PhenH(2)(NR(1))(2)][o-C(6)H(4)(CH=NR(2))]TiO(i)Pr [R(1) = 2,6-(i)Pr(2)C(6)H(3), R(2) = 2,6-Et(2)C(6)H(3) (3a); R(1) = 2,6-(i)Pr(2)C(6)H(3), 2,6-Me(2)C(6)H(3) (3b)], have been synthesized from the reactions of TiCl(2)(O(i)Pr)(2) with o-C(6)H(4)(CH=NR)Li [R = 2,6-(i)Pr(2)C(6)H(3), 2,6-Et(2)C(6)H(3), 2,6-Me(2)C(6)H(3)]. The symmetric complexes 2a-2c were obtained from the reactions of TiCl(2)(O(i)Pr)(2) with 2 equiv of the corresponding o-C(6)H(4)(CH=NR)Li followed by intramolecular C-C bond-forming reductive elimination and oxidative coupling processes, while the asymmetric complexes 2d-2e were formed from the reaction of TiCl(2)(O(i)Pr)(2) with two different types of o-C(6)H(4)(CH=NR)Li sequentially. The complexes 3a and 3b were also isolated from the reactions for complexes 2d and 2e. All complexes were characterized by (1)H and (13)C NMR spectroscopy, and the molecular structures of 2a, 2b, 2e, and 3a were determined by X-ray crystallography.     

Synthesis and characterization of new calcium phenylphosphonates and 4-carboxyphenylphosphonates

Three new calcium phenylphosphonates, CaC(6)H(5)PO(3).2H(2)O, Ca(3)(C(6)H(5)PO(3)H)(2)(C(6)H(5)PO(3))(2).4H(2)O, and CaC(6)H(5)PO(3).H(2)O, and two calcium 4-carboxyphenylphosphonates, Ca(HOOCC(6)H(4)PO(3)H)(2) and Ca(3)(OOCC(6)H(4)PO(3))(2).6H(2)O, were prepared. It was found that CaC(6)H(5)PO(3).2H(2)O transformed into previously known Ca(C(6)H(5)PO(3)H)(2) via Ca(3)(C(6)H(5)PO(3)H)(2)(C(6)H(5)PO(3))(2).4H(2)O in the presence of phenylphosphonic acid, and vice versa, Ca(C(6)H(5)PO(3)H)(2) turned into CaC(6)H(5)PO(3).2H(2)O in a weak basic medium. A similar relationship was found between Ca(HOOCC(6)H(4)PO(3)H)(2) and Ca(3)(OOCC(6)H(4)PO(3))(2).6H(2)O; i.e., Ca(3)(OOCC(6)H(4)PO(3))(2).6H(2)O transformed into Ca(HOOCC(6)H(4)PO(3)H)(2) in the presence of 4-carboxyphenylphosphonic acid. On the contrary, Ca(3)(OOCC(6)H(4)PO(3))(2).6H(2)O is formed from Ca(HOOCC(6)H(4)PO(3)H)(2) in the presence of ammonium as a weak base. The structure of Ca(HOOCC(6)H(4)PO(3)H)(2) was solved from X-ray powder diffraction data by an ab initio method using a FOX program. The compound is monoclinic, space group C2/c (No. 15), a = 49.218(3) A, b = 7.7609(4) A, c = 5.4452(3) A, beta = 128.119(3) degrees , and Z = 4. Its structure is one-dimensional with [Ca(2)(HOOCC(6)H(4)PO(3)H)(4)](infinity) ribbons forming basic building blocks. The ribbons are held together by hydrogen bonds between carboxylic groups.     

Regioselective functionalization of iminophosphoranes through Pd-mediated C-H bond activation: C-C and C-X bond formation

The orthopalladation of iminophosphoranes [R(3)P=N-C(10)H(7)-1] (R(3) = Ph(3) 1, p-Tol(3) 2, PhMe(2) 3, Ph(2)Me 4, N-C(10)H(7)-1 = 1-naphthyl) has been studied. It occurs regioselectively at the aryl ring bonded to the P atom in 1 and 2, giving endo-[Pd(μ-Cl)(C(6)H(4)-(PPh(2=N-1-C(10)H(7))-2)-κ-C,N](2) (5) or endo-[Pd(μ-Cl)(C(6)H(3)-(P(p-Tol)(2)=N-C(10)H(7)-1)-2-Me-5)-κ-C,N](2) (6), while in 3 the 1-naphthyl group is metallated instead, giving exo-[Pd(μ-Cl)(C(10)H(6)-(N=PPhMe(2))-8)-κ-C,N](2) (7). In the case of 4, orthopalladation at room temperature affords the kinetic exo isomer [Pd(μ-Cl)(C(10)H(6)-(N=PPh(2)Me)-8)-κ-C,N](2) (11exo), while a mixture of 11exo and the thermodynamic endo isomer [Pd(μ-Cl)(C(6)H(4)-(PPhMe=N-C(10)H(7)-1)-2)-κ-C,N](2) (11endo) is obtained in refluxing toluene. The heating in toluene of the acetate bridge dimer [Pd(μ-OAc)(C(10)H(6)-(N=PPh(2)Me)-8)-κ-C,N](2) (13exo) promotes the facile transformation of the exo isomer into the endo isomer [Pd(μ-OAc)(C(6)H(4)-(PPhMe=N-C(10)H(7)-1)-2)-κ-C,N](2) (13endo), confirming that the exo isomers are formed under kinetic control. Reactions of the orthometallated complexes have led to functionalized molecules. The stoichiometric reactions of the orthometallated complexes [Pd(μ-Cl)(C(10)H(6)-(N=PPhMe(2))-8)-κ-C,N](2) (7), [Pd(μ-Cl)(C(6)H(4)-(PPh(2)[=NPh)-2)](2) (17) and [Pd(μ-Cl)(C(6)H(3)-(C(O)N=PPh(3))-2-OMe-4)](2) (18) with I(2) or with CO results in the synthesis of the ortho-halogenated compounds [PhMe(2)P=N-C(10)H(6)-I-8] (19), [I-C(6)H(4)-(PPh(2)=NPh)-2] (21) and [Ph(3)P=NC(O)C(6)H(3)-I-2-OMe-5] (23) or the heterocycles [C(10)H(6)-(N=PPhMe(2))-1-(C(O))-8]Cl (20), [C(6)H(5)-(N=PPh(2)-C(6)H(4)-C(O)-2]ClO(4) (22) and [C(6)H(3)-(C(O)-1,2-N-PPh(3))-OMe-4]Cl (24).     

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.     

Template-assisted solvothermal synthesis of five copper(I)-thioantimonate(III) composites: crystal structures and optical and thermal properties of (C6N2H18)0.5Cu2SbS3, (C4N3H15)0.5Cu2SbS3, (C8N4H22)0.5Cu2SbS3, (C4N3H14)Cu3Sb2S5, and (C6)N4H20)0.5Cu3Sb2S5

The novel copper(I)-thioantimonates(III) (C(6)N(2)H(18))(0.5)Cu(2)SbS(3) (I) (C(6)N(2)H(16) = 1,6-diaminohexane), (C(4)N(3)H(15))(0.5)Cu(2)SbS(3) (II) (C(4)N(3)H(13) = diethylenetriamine), (C(8)N(4)H(22))(0.5)Cu(2)SbS(3) (III) (C(8)N(4)H(20) = 1,4-bis(2-aminoethyl)piperazine), (C(4)N(3)H(14))Cu(3)Sb(2)S(5) (IV) (C(4)N(3)H(13) = diethylenetriamine), and (C(6)N(4)H(20))(0.5)Cu(3)Sb(2)S(5) (V) (C(6)N(4)H(18) = triethylenetetramine) were synthesized under solvothermal conditions reacting Sb, Cu, and S with the amines. The compounds I-III belong to the RCu(2)SbS(3) structure family (R = amine) and are built up of trigonal SbS(3) pyramids and two CuS(3) moieties forming 6-membered (6 MR) and 10-membered (10 MR) rings. The rings are condensed yielding single layers which are joined into [Cu(2)SbS(3)](-) double layers via Cu-S bonds. The organic ions are located between the anionic layers, and the shortest interlayer distances are 7.8 Angstroms (I), 7.4 Angstroms (II), and 8.8 Angstroms (III). The structure of the novel inorganic-organic hybrid compound IV contains one SbS(3) group, one SbS(4) unit, two CuS(3) triangles, and one CuS(4) tetrahedron. These units are joined into four-membered (4 MR) and six-membered rings (6 MR) forming a hitherto unknown strong undulated layered (Cu(3)Sb(2)S(5))(-) anion. Anions and cations are arranged in a sandwichlike manner with an interlayer distance of 6.184 A. The new composite V contains an anion with the same chemical composition as compound IV, but the structure exhibits a unique and different network topology which is constructed by two SbS(3) pyramids, two CuS(3) triangles, and one CuS(4) tetrahedron. These units are joined into 6 MR which may be described as an inorganic graphene-like layer or as a 6(3) net. Two such layers are connected via Cu-S bonds into the final double layer. The interlayer distance amounts to 6.44 Angstroms. All compounds decompose in a more or less complex manner when heated in an inert atmosphere.     

Atmospheric chemistry of CF3CH2CH2OH: kinetics, mechanisms and products of Cl atom and OH radical initiated oxidation in the presence and absence of NOX

Relative rate techniques were used to study the kinetics of the reactions of Cl atoms and OH radicals with CF(3)CH(2)C(O)H and CF(3)CH(2)CH(2)OH in 700 Torr of N(2) or air diluent at 296 +/- 2 K. The rate constants determined were k(Cl+CF(3)CH(2)C(O)H) = (1.81 +/- 0.27) x 10(-11), k(OH+CF(3)CH(2)C(O)H) = (2.57 +/- 0.44) x 10(-12), k(Cl+CF(3)CH(2)CH(2)OH) = (1.59 +/- 0.20) x 10(-11), and k(OH+CF(3)CH(2)CH(2)OH) = (6.91 +/- 0.91) x 10(-13) cm(3) molecule(-1) s(-1). Product studies of the chlorine initiated oxidation of CF(3)CH(2)CH(2)OH in the absence of NO show the sole primary product to be CF(3)CH(2)C(O)H. Product studies of the chlorine initiated oxidation of CF(3)CH(2)CH(2)OH in the presence of NO show the primary products to be CF(3)CH(2)C(O)H (81%), HC(O)OH (10%), and CF(3)C(O)H. Product studies of the chlorine initiated oxidation of CF(3)CH(2)C(O)H in the absence of NO show the primary products to be CF(3)C(O)H (76%), CF(3)CH(2)C(O)OH (14%), and CF(3)CH(2)C(O)OOH (< or =10%). As part of this work, an upper limit of k(O(3)+CF(3)CH(2)CH(2)OH) < 2 x 10(-21) cm(3) molecule(-1) s(-1) was established. Results are discussed with respect to the atmospheric chemistry of fluorinated alcohols.     

Synthesis and structure of new carborane-substituted cyclotriphosphazenes

The reactions of [N(3)P(3)Cl(6)] with one, two, or three equivalents of the difunctional 1,2-closo-carborane C(2)B(10)H(10)[CH(2)OH](2) and K(2)CO(3) in acetone have been investigated. These reactions led to the new spiro-closo-carboranylphosphazenes gem-[N(3)P(3)Cl(6-2n)[(OCH(2))(2)C(2)B(10)H(10)](n)] (n=1 (1), 2 (2)) and the first fully carborane-substituted phosphazene gem-[N(3)P(3)[(OCH(2))(2)C(2)B(10)H(10)](3)] (3). A bridged product, non-gem-[N(3)P(3)Cl(4)[(OCH(2))(2)C(2)B(10)H(10)]] (4), was also detected. The reaction of the well-known spiro derivatives [N(3)P(3)Cl(2)(O(2)C(12)H(8))(2)] and [N(3)P(3)Cl(4)(O(2)C(12)H(8))] with the same carborane-diol and K(2)CO(3) in acetone gave the new compounds gem-[N(3)P(3)(O(2)C(12)H(8))(3-n)[(OCH(2))(2)C(2)B(10)H(10)](n)] (n=1 (5) or 2 (6), respectively), without signs of intra- or intermolecularly bridged species. Upon treatment with NEt(3) in acetone, compound 5 was converted into the corresponding nido-carboranylphosphazene. However, the reaction of gem-[N(3)P(3)(O(2)C(12)H(8))(2)[(OCH(2))(2)C(2)B(10)H(10)]] (5) with NEt(3) in ethanol instead of acetone proceeded in a different manner to give the new compound (NHEt(3))(2)[N(3)P(3)(O(2)C(12)H(8))(2)(O)[OCH(2)C(2)B(9)H(10)CH(2)OCH(2)CH(3)]] (7). For compounds with two 2,2'-dioxybiphenyl units, gem-[N(3)P(3)(O(2)C(12)H(8))(2)[(OCH(2))(2)C(2)B(10)H(10)]] (5), (NHEt(3))[N(3)P(3)(O(2)C(12)H(8))(2)[(OCH(2))(2)C(2)B(9)H(10)]] (8), and (NHEt(3))(2)[N(3)P(3)(O(2)C(12)H(8))(2)(O)[OCH(2)C(2)B(9)H(10)CH(2)OCH(2)CH(3)]] (7), a mixture of different stereoisomers may be expected. However, for 5 and 7 only the meso compounds seem to be formed, with the same (R,S)-configuration as in the precursor [N(3)P(3)Cl(2)(O(2)C(12)H(8))(2)]. The reaction of 5 to give 8 seems to proceed with a change of configuration at one phosphorus center, giving a racemic mixture. The crystal structures of the nido-carboranylphosphazenes 7 and 8 have been confirmed by X-ray diffraction methods.     

Lithium complexes supported by amine bis-phenolate ligands as efficient catalysts for ring-opening polymerization of L-lactide

Lithium complexes bearing dianionic amine bis(phenolate) ligands are described. Reactions of ligand precursors H(2)O(2)NN(Me), H(2)O(2)NN(Py) or H(2)O(2)NO(Me) [H(2)O(2)NN(Me)=Me(2)NCH(2)CH(2)N-(CH(2)-2-HO-3,5-C(6)H(2)((t)Bu)(2))(2); H(2)O(2)NN(Py)=(2-C(5)H(4)N)CH(2)N-(CH(2)-2-HO-3,5-C(6)H(2)((t)Bu)(2))(2); H(2)O(2)NO(Me)=MeOCH(2)CH(2)N-(CH(2)-2-HO-3,5-C(6)H(2)((t)Bu)(2))(2)] with 2.2 molar equivalents of (n)BuLi in diethylether afford (Li(2)O(2)NN(Me))(2) (1), (Li(2)O(2)NN(Py))(2) (2) and (Li(2)O(2)NO(Me))(2) (3) as tetra-nuclear lithium complexes. The crystalline solids of partially hydrolyzed product, (LiO(HO)NN(Py)) (4), were obtained from recrystallization of 2 in diethylether solution for three months. The synthesis of (LiO(HO)NO(Me))(2) (5) was carried out at ambient temperature by carefully layering a solution of water in hexane on top of a solution of 3 in Et(2)O. Crystalline solids of were obtained after two months. Molecular structures are reported for compounds 1, 3, 4 and 5. Compounds 1-3 show excellent catalytic activities toward the ring-opening polymerization of L-lactide in the presence of benzyl alcohol.     

Monocarbaborane anion chemistry. [COOH], [CH2OH] and [CHO] units as functional groups on ten-vertex monocarbaborane anionic compounds

B(10)H(14) reacts with para-C(6)H(4)(CHO)(COOH) in aqueous KOH solution to give the [nido-6-CB(9)H(11)-6-(C(6)H(4)-para-COOH)](-) anion 1, which undergoes cage closure with iodine in alkaline solution to give the [closo-2-CB(9)H(9)-2-(C(6)H(4)-para-COOH)](-) anion 2. Upon heating, anion 2 rearranges to form the [closo-1-CB(9)H(9)-1-(C(6)H(4)-para-COOH)](-) anion 3. Similarly, B(10)H(14) with glyoxylic acid OHCCOOH in aqueous KOH gives the [arachno-6-CB(9)H(13)-6-(COOH)](-) anion 4, which undergoes cage closure with iodine in alkaline solution to give the [closo-2-CB(9)H(9)-2-(COOH)](-) anion 5. Upon heating, anion 5 rearranges to give the [closo-1-CB(9)H(9)-1-(COOH)](-) anion 6. Reduction of the [COOH] anions 3 and 6 with diisobutylaluminium hydride gives the [CH(2)OH] hydroxy anions [closo-1-CB(9)H(9)-1-(C(6)H(4)-para-CH(2)OH)](-) and [closo-1-CB(9)H(9)-1-(CH(2)OH)](-) 8 respectively. The [closo-1-CB(9)H(9)-1-(C(6)H(4)-para-CH(2)OH)](-) anion 7 can also be made via isomerisation of the [closo-2-CB(9)H(9)-2-(C(6)H(4)-para-CH(2)OH)](-) anion 9, in turn obtained from the [nido-6-CB(9)H(11)-6-(C(6)H(4)-para-CH(2)OH)](-) anion 10, which is obtained from the reaction of B(10)H(14) with terephthaldicarboxaldehyde, C(6)H(4)-para-(CHO)(2), in aqueous KOH solution. Oxidation of the hydroxy anions 7 and 8 with pyridinium dichromate gives the aldehydic [closo-1-CB(9)H(9)-1-(C(6)H(4)-para-CHO)](-) anion 11 and the aldehydic [closo-1-CB(9)H(9)-1-(CHO)](-) anion 12 respectively, characterised as their 2,4-dinitrophenylhydrazone derivatives, the [closo-1-CB(9)H(9)-1-C(6)H(4)-para-CH=N-NHC(6)H(3)(NO(2))(2)](-) anion 13 and the [closo-1-CB(9)H(9)-1-CH=N-NHC(6)H(3)(NO(2))(2)](-) anion respectively.     

Atmospheric chemistry of C2F5CH2OCH3 (HFE-365mcf)

FTIR smog chamber techniques were used to measure k(Cl + C(2)F(5)CH(2)OCH(3)) = (2.52 ± 0.37) × 10(-11) and k(OH + C(2)F(5)CH(2)OCH(3)) = (5.78 ± 1.02) × 10(-13) cm(3) molecule(-1) s(-1) in 700 Torr of air diluent at 296 ± 1 K. The atmospheric lifetime of C(2)F(5)CH(2)OCH(3) is estimated to be 20 days. Reaction of chlorine atoms with C(2)F(5)CH(2)OCH(3) proceeds 18 ± 2% at the -CH(2)- group and 82 ± 2% at the -CH(3) group. Reaction of OH radicals with C(2)F(5)CH(2)OCH(3) proceeds 44 ± 5% at the -CH(2)- group and 56 ± 5% at the -CH(3) group. The atmospheric fate of C(2)F(5)CH(2)OCH(2)O radicals is reaction with O(2) to give C(2)F(5)CH(2)OCHO. The atmospheric fate of C(2)F(5)CH(O)OCH(3) radicals is C-C bond-cleavage to give C(2)F(5) radicals and CH(3)OCHO (methyl formate). The infrared spectrum was recorded and used to estimate a global warming potential of 6 (100 year time horizon) for C(2)F(5)CH(2)OCH(3).     

Energetics of cresols and of methylphenoxyl radicals

Combustion calorimetry studies were used to determine the standard molar enthalpies of formation of o-, m-, and p-cresols, at 298.15 K, in the condensed state as Delta(f)H(m) degrees (o-CH(3)C(6)H(4)OH,cr) = -204.2 +/- 2.7 kJ.mol(-1), Delta(f)H(m) degrees (m-CH(3)C(6)H(4)OH,l) = -196.6 +/- 2.1 kJ.mol(-1), and Delta(f)H(m) degrees (p-CH(3)C(6)H(4)OH,cr) = -202.2 +/- 3.0 kJ.mol(-1). Calvet drop calorimetric measurements led to the following enthalpy of sublimation and vaporization values at 298.15 K: Delta(sub)H(m) degrees (o-CH(3)C(6)H(4)OH) = 73.74 +/- 0.46 kJ.mol(-1), Delta(vap)H(m) degrees (m-CH(3)C(6)H(4)OH) = 64.96 +/- 0.69 kJ.mol(-1), and Delta(sub)H(m) degrees (p-CH(3)C(6)H(4)OH) = 73.13 +/- 0.56 kJ.mol(-1). From the obtained Delta(f)H(m) degrees (l/cr) and Delta(vap)H(m) degrees /Delta(sub)H(m) degrees values, it was possible to derive Delta(f)H(m) degrees (o-CH(3)C(6)H(4)OH,g) = -130.5 +/- 2.7 kJ.mol(-1), Delta(f)H(m) degrees (m-CH(3)C(6)H(4)OH,g) = -131.6 +/- 2.2 kJ.mol(-1), and Delta(f)H(m) degrees (p-CH(3)C(6)H(4)OH,g) = -129.1 +/- 3.1 kJ.mol(-1). These values, together with the enthalpies of isodesmic and isogyric gas-phase reactions predicted by the B3LYP/cc-pVDZ, B3LYP/cc-pVTZ, B3P86/cc-pVDZ, B3P86/cc-pVTZ, MPW1PW91/cc-pVTZ, CBS-QB3, and CCSD/cc-pVDZ//B3LYP/cc-pVTZ methods, were used to obtain the differences between the enthalpy of formation of the phenoxyl radical and the enthalpies of formation of the three methylphenoxyl radicals: Delta(f)H(m) degrees (C(6)H(5)O*,g) - Delta(f)H(m) degrees (o-CH(3)C(6)H(4)O*,g) = 42.2 +/- 2.8 kJ.mol(-1), Delta(f)H(m) degrees (C(6)H(5)O*,g) - Delta(f)H(m) degrees (m-CH(3)C(6)H(4)O*,g) = 36.1 +/- 2.4 kJ.mol(-1), and Delta(f)H(m) degrees (C(6)H(5)O*,g) - Delta(f)H(m) degrees (p-CH(3)C(6)H(4)O*,g) = 38.6 +/- 3.2 kJ.mol(-1). The corresponding differences in O-H bond dissociation enthalpies were also derived as DH degrees (C(6)H(5)O-H) - DH degrees (o-CH(3)C(6)H(4)O-H) = 8.1 +/- 4.0 kJ.mol(-1), DH degrees (C(6)H(5)O-H) - DH degrees (m-CH(3)C(6)H(4)O-H) = 0.9 +/- 3.4 kJ.mol(-1), and DH degrees (C(6)H(5)O-H) - DH degrees (p-CH(3)C(6)H(4)O-H) = 5.9 +/- 4.5 kJ.mol(-1). Based on the differences in Gibbs energies of formation obtained from the enthalpic data mentioned above and from published or calculated entropy values, it is concluded that the relative stability of the cresols varies according to p-cresol < m-cresol < o-cresol, and that of the radicals follows the trend m-methylphenoxyl < p-methylphenoxyl < o-methylphenoxyl. It is also found that these tendencies are enthalpically controlled.     

Photodissociation of S atom containing amino acid chromophores

Photodissociation of 3-(methylthio)propylamine and cysteamine, the chromophores of S atom containing amino acid methionine and cysteine, respectively, was studied separately in a molecular beam at 193 nm using multimass ion imaging techniques. Four dissociation channels were observed for 3-(methylthio)propylamine, including (1) CH(3)SCH(2)CH(2)CH(2)NH(2)-->CH(3)SCH(2)CH(2)CH(2)NH+H, (2) CH(3)SCH(2)CH(2)CH(2)NH(2)-->CH(3)+SCH(2)CH(2)CH(2)NH(2), (3) CH(3)SCH(2)CH(2)CH(2)NH(2)-->CH(3)S+CH(2)CH(2)CH(2)NH(2), and (4) CH(3)SCH(2)CH(2)CH(2)NH(2)-->CH(3)SCH(2)+CH(2)CH(2)NH(2). Two dissociation channels were observed from cysteamine, including (5) HSCH(2)CH(2)NH(2)-->HS+CH(2)CH(2)NH(2) and (6) HSCH(2)CH(2)NH(2)-->HSCH(2)+CH(2)NH(2). The photofragment translational energy distributions suggest that reaction (1) and parts of the reactions (2), (3), (5) occur on the repulsive excited states. However, reaction (4), (6) occur only after the internal conversion to the electronic ground state. Since the dissociation from an excited state with a repulsive potential energy surface is very fast, it would not be quenched completely even in the condensed phase. Our results indicate that reactions following dissociation may play an important role in the UV photochemistry of S atom containing amino acid chromophores in the condensed phase. A comparison with the potential energy surface from ab initio calculations and branching ratios from RRKM calculations was made.     

Syntheses and structures of the infinite chain compounds Cs(4)Ti(3)Se(13), Rb(4)Ti(3)S(14), Cs(4)Ti(3)S(14), Rb(4)Hf(3)S(14), Rb(4)Zr(3)Se(14), Cs(4)Zr(3)Se(14), and Cs(4)Hf(3)Se(14)

The alkali metal/group 4 metal/polychalcogenides Cs(4)Ti(3)Se(13), Rb(4)Ti(3)S(14), Cs(4)Ti(3)S(14), Rb(4)Hf(3)S(14), Rb(4)Zr(3)Se(14), Cs(4)Zr(3)Se(14), and Cs(4)Hf(3)Se(14) have been synthesized by means of the reactive flux method at 823 or 873 K. Cs(4)Ti(3)Se(13) crystallizes in a new structure type in space group C(2)(2)-P2(1) with eight formula units in a monoclinic cell at T = 153 K of dimensions a = 10.2524(6) A, b = 32.468(2) A, c = 14.6747(8) A, beta = 100.008(1) degrees. Cs(4)Ti(3)Se(13) is composed of four independent one-dimensional [Ti(3)Se(13)(4-)] chains separated by Cs(+) cations. These chains adopt hexagonal closest packing along the [100] direction. The [Ti(3)Se(13)(4-)] chains are built from the face- and edge-sharing of pentagonal pyramids and pentagonal bipyramids. Formal oxidation states cannot be assigned in Cs(4)Ti(3)Se(13). The compounds Rb(4)Ti(3)S(14), Cs(4)Ti(3)S(14), Rb(4)Hf(3)S(14), Rb(4)Zr(3)Se(14), Cs(4)Zr(3)Se(14), and Cs(4)Hf(3)Se(14) crystallize in the K(4)Ti(3)S(14) structure type with four formula units in space group C(2)(h)()(6)-C2/c of the monoclinic system at T = 153 K in cells of dimensions a = 21.085(1) A, b = 8.1169(5) A, c = 13.1992(8) A, beta = 112.835(1) degrees for Rb(4)Ti(3)S(14);a = 21.329(3) A, b = 8.415(1) A, c = 13.678(2) A, beta = 113.801(2) degrees for Cs(4)Ti(3)S(14); a = 21.643(2) A, b = 8.1848(8) A, c = 13.331(1) A, beta = 111.762(2) degrees for Rb(4)Hf(3)S(14); a = 22.605(7) A, b = 8.552(3) A, c = 13.880(4) A, beta = 110.919(9) degrees for Rb(4)Zr(3)Se(14); a = 22.826(5) A, b = 8.841(2) A, c = 14.278(3) A, beta = 111.456(4) degrees for Cs(4)Zr(3)Se(14); and a = 22.758(5) A, b = 8.844(2) A, c = 14.276(3) A, beta = 111.88(3) degrees for Cs(4)Hf(3)Se(14). These A(4)M(3)Q(14) compounds (A = alkali metal; M = group 4 metal; Q = chalcogen) contain hexagonally closest-packed [M(3)Q(14)(4-)] chains that run in the [101] direction and are separated by A(+) cations. Each [M(3)Q(14)(4-)] chain is built from a [M(3)Q(14)] unit that consists of two MQ(7) pentagonal bipyramids or one distorted MQ(8) bicapped octahedron bonded together by edge- or face-sharing. Each [M(3)Q(14)] unit contains six Q(2)(2-) dimers, with Q-Q distances in the normal single-bond range 2.0616(9)-2.095(2) A for S-S and 2.367(1)-2.391(2) A for Se-Se. The A(4)M(3)Q(14) compounds can be formulated as (A(+))(4)(M(4+))(3)(Q(2)(2-))(6)(Q(2-))(2).