C6F5Xe]+ and [C6F5XeNCCH3]+ salts of the weakly coordinating borate anions, [BY4]- (Y = CN, CF3, or C6F5)

New examples of [C6F5Xe]+ salts of the weakly coordinating [BY4]- (Y = CN, CF3, or C6F5) anions were synthesized by metathesis of [C6F5Xe][BF4] with MI[BY4] (MI = K or Cs; Y = CN, CF3, or C6F5) in CH3CN at -40 degrees C, and were crystallized from CH2Cl2 or from a CH2Cl2/CH3CN solvent mixture. The low-temperature (-173 degrees C) X-ray crystal structures of the [C6F5Xe]+ cation and of the [C6F5XeNCCH3]+ adduct-cation are reported for [C6F5Xe][B(CF3)4], [C6F5XeNCCH3][B(CF3)4], [C6F5Xe][B(CN)4], and [C6F5XeNCCH3][B(C6F5)4]. The [C6F5Xe]+ cation, in each structure, interacts with either the anion or the solvent, with the weakest cation-anion interactions occurring for the [B(CF3)4]- anion. The solid-state Raman spectra of the [C6F5Xe]+ and [C6F5XeNCCH3]+ salts have been assigned with the aid of electronic structure calculations. Gas-phase thermodynamic calculations show that the donor-acceptor bond dissociation energy of [C6F5XeNCCH3]+ is approximately half that of [FXeNCCH3]+. Coordination of CH3CN to [C6F5Xe]+ is correlated with changes in the partial charges on mainly Xe, the ipso-C, and N, that is, the partial charge on Xe increases and those on the ipso-C and N decrease upon coordination, typifying a transition from a 2c-2e to a 3c-4e bond.     

Syntheses of [F5TeNH3][AsF6], [F5TeN(H)Xe][AsF6], and F5TeNF2 and characterization by multi-NMR and Raman spectroscopy and by electronic structure calculations: the X-ray crystal structures of alpha- and beta-F5TeNH2, [F5TeNH3][AsF6], and [F5TeN(H)Xe][AsF6

The salt, [F5TeN(H)Xe][AsF6], has been synthesized in the natural abundance and 99.5% 15N-enriched forms. The F5TeN(H)Xe+ cation has been obtained as the product of the reactions of [F5TeNH3][AsF6] with XeF2 (HF and BrF5 solvents) and F5TeNH2 with [XeF][AsF6] (HF solvent) and characterized in solution by 129Xe, 19F, 125Te, 1H, and 15N NMR spectroscopy at -60 to -30 degrees C. The orange [F5TeN(H)Xe][AsF6] and colorless [F5TeNH3][AsF6] salts were crystallized as a mixture from HF solvent at -35 degrees C and were characterized by Raman spectroscopy at -165 degrees C and by X-ray crystallography. The crystal structure of the low-temperature phase, alpha-F5TeNH2, was obtained by crystallization from liquid SO2 between -50 and -70 degrees C and is fully ordered. The high-temperature phase, beta-F5TeNH2, was obtained by sublimation at room temperature and exhibits a 6-fold disorder. Decomposition of [F5TeN(H)Xe][AsF6] in the solid state was rapid above -30 degrees C. The decomposition of F5TeN(H)Xe+ in HF and BrF5 solution at -33 degrees C proceeded by fluorination at nitrogen to give F5TeNF2 and Xe gas. Electronic structure calculations at the Hartree-Fock and local density-functional theory levels were used to calculate the gas-phase geometries, charges, Mayer bond orders, and Mayer valencies of F5TeNH2, F5TeNH3+, F5TeN(H)Xe+, [F5TeN(H)Xe][AsF6], F5TeNF2, and F5TeN2- and to assign their experimental vibrational frequencies. The F5TeN(H)Xe+ and the ion pair, [F5TeN(H)Xe][AsF6], systems were also calculated at the MP2 and gradient-corrected (B3LYP) levels.     

The syntheses of carbocations by use of the noble-gas oxidant, [XeOTeF5][Sb(OTeF5)6]: the syntheses and characterization of the CX3+ (X = Cl, Br, OTeF5) and CBr(OTeF5)2+ cations and theoretical studies of CX3+ and BX3 (X = F, Cl, Br, I, OTeF5)

The CCl(3)(+) and CBr(3)(+) cations have been synthesized by oxidation of a halide ligand of CCl(4) and CBr(4) at -78 degrees C in SO(2)ClF solvent by use of [XeOTeF(5)][Sb(OTeF(5))(6)]. The CBr(3)(+) cation reacts further with BrOTeF(5) to give CBr(OTeF(5))(2)(+), C(OTeF(5))(3)(+), and Br(2). The [XeOTeF(5)][Sb(OTeF(5))(6)] salt was also found to react with BrOTeF(5) in SO(2)ClF solvent at -78 degrees C to give the Br(OTeF(5))(2)(+) cation. The CCl(3)(+), CBr(3)(+), CBr(OTeF(5))(2)(+), C(OTeF(5))(3)(+), and Br(OTeF(5))(2)(+) cations and C(OTeF(5))(4) have been characterized in SO(2)ClF solution by (13)C and/or (19)F NMR spectroscopy at -78 degrees C. The X-ray crystal structures of the CCl(3)(+), CBr(3)(+), and C(OTeF(5))(3)(+) cations have been determined in [CCl(3)][Sb(OTeF(5))(6)], [CBr(3)][Sb(OTeF(5))(6)].SO(2)ClF, and [C(OTeF(5))(3)][Sb(OTeF(5))(6)].3SO(2)ClF at -173 degrees C. The CCl(3)(+) and CBr(3)(+) salts were stable at room temperature, whereas the CBr(n)(OTeF(5))(3-n)(+) salts were stable at 0 degrees C for several hours. The cations were found to be trigonal planar about carbon, with the CCl(3)(+) and CBr(3)(+) cations showing no significant interactions between their carbon atoms and the fluorine atoms of the Sb(OTeF(5))(6)(-) anions. In contrast, the C(OTeF(5))(3)(+) cation interacts with an oxygen of each of two SO(2)ClF molecules by coordination along the three-fold axis of the cation. The solid-state Raman spectra of the Sb(OTeF(5))(6)(-) salts of CCl(3)(+) and CBr(3)(+) have been obtained and assigned with the aid of electronic structure calculations. The CCl(3)(+) cation displays a well-resolved (35)Cl/(37)Cl isotopic pattern for the symmetric CCl(3) stretch. The energy-minimized geometries, natural charges, and natural bond orders of the CCl(3)(+), CBr(3)(+), CI(3)(+), and C(OTeF(5))(3)(+) cations and of the presently unknown CF(3)(+) cation have been calculated using HF and MP2 methods have been compared with those of the isoelectronic BX(3) molecules (X = F, Cl, Br, I, and OTeF(5)). The (13)C and (11)B chemical shifts for CX(3)(+) (X = Cl, Br, I) and BX(3) (X = F, Cl, Br, I) were calculated by the GIAO method, and their trends were assessed in terms of paramagnetic contributions and spin-orbit coupling.     

Photochemical synthesis,reactivity, and electrochemical properties of [CpFeP2L]+ cations; (Cp = C5H5, C5Me5; L = Co vs. CH3CN; P = phosphine or phosphite)

Photolytic replacement of the arene ligand in the cations [CpFe(p-xylene)]⁺ (Cp = C₅Me₅) by P(OMe)₃ ligands is only possible when a sensitizer (acetone or anthracene) is present and leads to CpFe⁺{P(OMe₃)}₃. Photoextrusion of one phosphite ligand from [C₅R₅Fe{P(OMe)₃}₃]⁺ (R = H, Me) or of the carbonyl from [C₅R₅Fe(P ⌢ P)(CO)]⁺ (R = H, Me; P ⌢ P = dppm, dppe) in CH₃CN leads to CH₃CN complexes which are reversibly oxidized.     

Synthesis of the new, weakly coordinating anions [RB(C6F5)3]- (R = CH2Me, CHMe2, CH2CMe3); utilization of [HNMe2Ph][Me3CCH2B(C6F5)3] to activate zirconocene catalysts for propylene polymerization

The compound [HNMe2Ph][NpB(C6F5)3](Np =(CH3)3CCH2) reacts with dimethylzirconocenes to give active propylene polymerization catalysts which are significantly more active and give higher molecular weight polypropylene than do the catalysts obtained using B(C6F5)3; the [NpB(C6F5)3]- anion is for steric reasons more weakly coordinating than is [MeB(C6F5)3]-.     

Syntheses and solid-state and solution structures of [Ba[(C5Me5)2Ti2F7]2(hmpa)] and [Ba8Ti6F30I2(C5Me5)6(hmpa)6][I3]2

The complexes [Ba[(C5Me5)2Ti2F7]2(hmpa)].(THF), 1.hmpa.(THF), and [Ba8Ti6F30I2(C5Me5)6(hmpa)6][I3]2.10(THF), 2[I3]2.10(THF), were prepared from [Hdmpy](+)[(C5Me5)2Ti2F7]- (dmpy = 2,6-dimethylpyridine), BaI2, and hmpa (hmpa = hexamethylphosphoramide). They were characterized by 1H and 19F NMR and IR spectroscopy and examined by single-crystal X-ray crystallography. The complexation equilibrium of the barium ion in 1 with hmpa and the dynamics of the barium ion moving on the fluorine surfaces of [(C5Me5)2Ti2F7]- in 1.hmpa have been studied by variable-temperature 19F NMR spectroscopy. The core of the complex 2[I3]2.10(THF) resembles the basic structural unit of the cubic perovskite.     

Weakly coordinating nature of a carborane cage bearing different halogen atoms. Synthesis and structural characterization of icosahedral mixed halocarborane anions, 1-H-CB11Y5X6- (X, Y = Cl, Br, I)

Mixed halocarborane anions, 1-H-CB11Y5X6- (X, Y = Cl, Br, I), have been prepared by treatment of [Me3NH][1-H-CB11H5X6] (X = Cl, Br, I) with proper halogenating reagents at 180-220 degrees C in a sealed tube in high yield. These new anions are fully characterized by 1H, 13C, and 11B NMR, IR, and negative-ion MALDI MS spectroscopy. Some are further confirmed by single-crystal X-ray analyses. The weakly coordinating nature of these anions is probed by 29Si chemical shifts of the resulting Pri3Si(1-H-CB11Y5X6) compounds. The results suggest that the coordinating ability of these anions is mainly dependent on the substituents at 7-12 positions (namely, X atoms), and the contribution from the upper belt substituents Y is relatively small. These suggestions are consistent with the results obtained from the structural study of silver salts of mixed halo- and perhalocarborane anions.     

Syntheses and characterization of the metal maleonitrilediselenolates [K([2.2.2]-cryptand)]2[M(Se2C2(CN)2)2] (M = Ni, Pd, Pt) and [Ni(dmf)(5)Cl]2[Ni(Se2C2(CN)2)2

Reaction of KNH(2), K(2)Se, Se, [2.2.2]-cryptand, and a metal source yields the metal bis(maleonitrilediselenolates) [K([2.2.2]-cryptand)](2)[M(Se(2)C(2)(CN)(2))(2)] (M = Ni, 1; Pd, 2, Pt, 3). These compounds are isostructural and crystallize with four formula units in the monoclinic space group P2(1)/c in cells at T = 153 K with parameters (a (A), b (A), c (A), beta (deg), V (A(3))) of 12.220(1), 15.860(2), 15.306(1), 107.64(2), 2827(1) for 1; 12.291(1), 15.669(1), 15.548(1), 108.55(1), 2839(1) for 2; and 12.292(3), 15.671(3), 15.569(3), 108.59(3), 2842(1) for 3. The cation of 1 has been substituted to yield [Ni(dmf)(5)Cl](2)[Ni(Se(2)C(2)(CN)(2))(2)] (4). [Ni(dmf)(5)Cl](2)[Ni(Se(2)C(2)(CN)(2))(2)] (4) crystallizes with one molecule in the triclinic space group P1 in a cell with parameters (T = 153 K) of a = 8.842(2) A, b =13.161(3) A, c = 13.831(3) A, alpha = 110.08(3) degrees, beta = 95.23(3) degrees, gamma = 93.72(3) degrees, V = 1484(1) A(3). The electronic absorption and infrared spectra are characteristic of metal maleonitrilediselenolates. Cyclic voltammetry shows that the maleonitrilediselenolate (mns) complexes are more easily oxidized than their maleonitriledithiolate (mnt) analogues.     

Synthesis and characterization of A4[Re6Q8L6]@SiO2 red-emitting silica nanoparticles based on Re6 metal atom clusters (A = Cs or K, Q = S or Se, and L = OH or CN)

Metal atom clusters constitute very promising candidates as luminophores for applications in biotechnology because they are nanosized entities offering robust luminescence in the near-infrared field (NIR). However, they cannot be used as prepared for biological applications because of potential toxic effects and quenching of the clusters' luminescence in aqueous media, and they therefore need to be dispersed in a biocompatible matrix. We describe herein the encapsulation of octahedral rhenium clusters, denoted as A(4)[Re(6)Q(8)L(6)] (A = Cs or K, Q = S or Se, and L = OH or CN), in silica nanoparticles by a water-in-oil microemulsion process, paying particular attention to the clusters' stability. The obtained A(4)[Re(6)Q(8)L(6)]@SiO(2) nanoparticles are 30 nm in size with good monodispersity and a perfectly spherical shape, as shown by scanning electron microscopy (SEM). The presence of cluster units inside the silica matrix was evidenced by scanning transmission electron microscopy in annular dark-field mode (ADF-STEM). From the point of view of their optical properties, the A(4)[Re(6)Q(8)L(6)]@SiO(2) nanoparticles show red and NIR emission under UV excitation, even when dispersed in water. The evolution of the structural and luminescence properties of clusters before and after encapsulation was followed by Raman and photoluminescence spectroscopy.     

A Nonempirical Quantum-Chemical Study and Natural Bond Orbital Analysis of C6H5XCY3 Species (X = SO or SO2, Y = H or F)

The potential functions of internal rotation about the C² _sp—S bonds for C₆H₅XCY₃ species (X = SO or SO₂, Y = H or F) have been obtained at the MP2 (full)/6-31+G(d) level of ab initio theory. It is found that the spatial structures with the plane of C² _sp—S—C³ _sp bonds, which is near perpendicular to the benzene ring plane, are the energy-favourable conformations. The values of the rotational barrier about the C² _sp—S bond are equal to (kJ/mole): 21.2 (C₆H₅SOCH₃), 29.0 (C₆H₅SOCF₃), 20.4 (C₆H₅SO₂CH₃), and 28.2 (C₆H₅SO₂CF₃). On the basis of the Natural Bond Orbital (NBO) analysis results, it has been revealed that the double S=O bond is a strongly polarized covalent -bond, whereas -bond electrons practically are localized on the oxygen atom. The S=O bond order for aromatic sulfoxides and sulphones is mainly caused by hyperconjugational interactions according to the LP(O) ^*(S—C_ipso) and LP(O) ^*(S—C _Y ) mechanisms. In sulphones there is also the additional mechanism of hyperconjugational interactions such as LP(O^{1 *}(S—O²) and LP(O²) ^*(S—O¹). With the replacement of one hydrogen atom on the —XCY₃ group, the charge loss of the unsubstituted benzene molecule increases: —SOCH₃ < —SO₂CH₃ < — SOCF₃ < —SO₂CF₃. The substitution of the —CH₃ group for the —CF₃ group weakly influences the charge value on the sulfur atom but effects the acceptor characteristics of the substituent to a greater extent than the variation of the sulfur atom coordination.     

Reaction paths of the [2+2] cycloaddition of X=C=Y molecules (X, Y=S or O or CH2). Ab initio study

The reaction paths of [2+2] cycloaddition of the X=C=Y cumulenes were modeled at the MP2/aug-cc-pVDZ level. Cycloadditions of allene and CO2, CS2, or OCS lead in part to the same four-membered products as dimerizations of either ketene or thioketene or addition of ketene and thioketene, respectively. All the reactions studied are concerted and mostly asynchronous. The majority of the allene cycloadditions studied are endoergic and proceed with much higher activation barriers than do the alternative (thio)ketene additions. In comparison with the energy of the substrates, the four-membered cycles incorporating S-atoms are stabilized more than the analogous structures with O-atoms built into the rings. There are also some products that are thermodynamically disfavored, yet seem to be obtainable thanks to a relatively low barrier of the reaction. The AIM analysis of the electron density distribution in the transition state structures allowed distinguishing pericyclic from pseudopericyclic and nonplanar-pseudopericyclic types of reaction.     

Robust S4⋅⋅⋅O Supramolecular Synthons: Structures of Radical-Radical Cocrystals [p-XC6F4CNSSN]2[TEMPO] (X=F,Cl, Br,I, CN)

Cocrystallization of the dithiadiazolyl (DTDA) radicals p-XC₆F₄CNSSN (X=F, Cl, Br, I, CN) with TEMPO afforded the 2 : 1 cocrystals [p-XC₆F₄CNSSN]₂[TEMPO] ( 1 – 5 ) whose structures all reflect a common S₄⋅⋅⋅O supramolecular motif. The nature of this interaction was probed by DFT calculations (M06/aug-cc-pVDZ) on 1 which revealed that the enthalpy of formation of the [C₆F₅CNSSN]₂[TEMPO] supramolecular motif from [C₆F₅CNSSN]₂ and TEMPO is substantial (−54.0 kJ mol⁻¹). Electronic structure calculations revealed a TEMPO-based doublet S= configuration as the ground state with limited spin density on the DTDA rings (2.4 %). The corresponding spin quartet state is +78.9 kJ mol⁻¹ higher in energy. An atoms-in-molecules analysis reveals four bond critical points (BCPs) between the TEMPO O and the DTDA S atoms as well as additional BCPs between selected DTDA S atoms and methyl H atoms of the TEMPO molecule. Herein, the structures of 2 – 5 are considered within the context of a hierarchical view of competing and complementary intermolecular interactions; in particular, the established supramolecular CN⋅⋅⋅S−S synthon is sacrificed in order to form the new S₄⋅⋅⋅O interaction.     

Magnetic studies on hexahalorhenate(IV) salts of ferrocenium cations [Fe(C5R5)2]2[ReX6] (R = H, CH3; X = Cl, Br, I)

The hexahalorhenate(IV) salts of formula [Fe(C5H5)2]2[ReX6], with X = Cl (1), Br (2), and I (3), and [Fe(C5Me5)2]2[ReX6], with X = Cl (4), Br (5), and I (6) ([Fe(C5Me5)2]+ = decamethylferrocenium cation), have been synthesized and the structures of 1, 2, and 4 determined by single-crystal X-ray diffraction. 1, 2, and 4 crystallize in the orthorhombic system, space groups Pbca (1 and 2) and Ibam (4), with a = 14.099(2) A, b = 16.125(2) A, and c = 22.133(15) A, for 1, a = 14.317(3) A, b = 16.848(3) A, and c = 22.099(2) A for 2, and a = 15.8583(5) A, b = 15.9368(5) A, and c = 16.9816(6) A for 4. The three structures are made up of discrete [ReX6]2- anions and ferrocenium cations held together by electrostatic forces. There are anion-anion contacts in 1 and 2 but only through one direction. The [ReX6]2- octahedra are arranged along the y axis forming chains of Re and X atoms, -Re-X...X-Re-X...X-Re-, where the intermolecular X...X distances are shorter than the van der Waals distances. A somewhat greater separation between the anions occurs in 4. The magnetic properties of 1-6 were investigated in the temperature range 2.0-300 K. 1, 2, 4, and 5 exhibit an antiferromagnetic coupling between the anions, whereas a ferromagnetic coupling between anions and cations is the dominant interaction in 3. 6 behaves as a magnetically isolated compound, its susceptibility being the simple addition of the independent contributions of the uncoupled paramagnetic cations and anions.     

The synthesis and crystal structures of halogenated tolans p-X-C6H4-C[triple bond]C-C6F5 and p-X-C6F4-C[triple bond]C-C6H5(X=F, Cl, Br, I)

A series of halogenated, partially fluorinated tolans of general formula p-X-C6H4-C[triple bond]C-C6F5[X=I (1), Br (2), Cl (3), F (4)] and p-X-C6F4-C[triple bond]C-C6H5[X=I (5), Br (6)] have been prepared via palladium-catalysed Sonogashira cross-coupling, or for X=Cl (7), by nucleophilic aromatic substitution reactions. The single-crystal X-ray structures of 1-3 and 5-6 have been determined. The structures reveal that the molecular packing is characterized by either arene-perfluoroarene interactions (3), or halogen-halogen interactions (isomorphous 1 and 2), or neither (isomorphous 5 and 6). The structure of represents the first fully determined crystal structure of a compound that contains a halogen atom other than fluorine, in which arene-perfluoroarene interactions are present.     

Tetrachloro- and tetrabromoarsonium(V) cations: raman and 75As, 19F NMR spectroscopic characterization and X-ray crystal structures of [AsCl4][As(OTeF5)6] and [AsBr4][AsF(OTeF5)5]

The salts [AsX4][As(OTeF5)6] and [AsBr4][AsF(OTeF5)5] (X = Cl, Br) have been prepared by oxidation of AsX3 with XOTeF5 in the presence of the OTeF5 acceptors As(OTeF5)5 and AsF(OTeF5)4. The mixed salts [AsCl4][Sb(OTeF5)6-nCl(n-2)] and [AsCl4][Sb(OTeF5)6-nCl(n)] (n > or = 2) have also been prepared. The AsBr4+ cation has been fully structurally characterized for the first time in SO2ClF solution by 75As NMR spectroscopy and in the solid state by a single-crystal X-ray diffraction study of [AsBr4][AsF(OTeFs)5]: P1, a = 9.778(4) A, b = 17.731(7) A, c = 18.870(8) A, alpha = 103.53(4)degrees, beta = 103.53(4) degrees, gamma = 105.10(4) degrees, V = 2915(2) A3, Z = 4, and R1 = 0.0368 at -183 degrees C. The crystal structure determination and solution 75As NMR study of the related [AsCl4][As(OTeF5)6] salt have also been carried out: [AsCl4][As(OTeF5)6], R3, a = 9.8741(14) A, c = 55.301(11) A, V= 4669(1) A3, Z = 6, and R1 = 0.0438 at -123 degrees C; and R3, a = 19.688(3) A, c = 55.264(11) A, V= 18552(5) A3, Z = 24, and R1 = 0.1341 at -183 degrees C. The crystal structure of the As(OTeF5)6- salt reveals weaker interactions between the anion and cation than in the previously known AsF6- salt. The AsF(OTeF5)5- anion is reported for the first time and is also weakly coordinating with respect to the AsBr4+ cation. Both cations are undistorted tetrahedra with bond lengths of 2.041(5)-2.056(3) A for AsCl4+ and 2.225(2)-2.236(2) A for AsBr4+. The Raman spectra are consistent with undistorted AsX4+ tetrahedra and have been assigned under Td point symmetry. The 35Cl/37Cl isotope shifts have been observed and assigned for AsCl4+, and the geometrical parameters and vibrational frequencies of all known and presently unknown PnX4+ (Pn = P, As, Sb, Bi; X = F, Cl, Br, I) cations have been calculated using density functional theory methods.     

The preparations and properties of tris(perfluoroorgano)bismuth compounds Bi(Rf)3 (Rf = CF3, C2F5, n-C3F7, n-C4F9, n-C6F13, n-C8 F17, C6F5)

Tris(perfluoroorgano)bismuth compounds Bi(R_f)₃ (R_f = CF₃, C₂F₅, n-C₃F₇, n-C₄F₉, n-C₆F₁₃, n-C₈F₁₇, C₆F₅) are easily prepared in high yields from the reactions of perfluoroorganocadmium complexes with BiCl₃, or BiBr₃ in aprotic solvents. The perfluoroorganobismuth halides intermediates in these reactions have been detected by NMR spectroscopy.     

Bimetallic cyanide-bridged complexes based on the photochromic nitroprusside anion and paramagnetic metal complexes. Syntheses, structures, and physical characterization of the coordination compounds [Ni(en)2]4[Fe(CN)5NO]2[Fe(CN)6]x5H2O, [Ni(en)2][Fe(CN)5NO]x3H2O, [Mn(3-MeOsalen)(H2O)]2[Fe(CN)5NO], and [Mn(5-Brsalen)]2[Fe(CN)5NO

The synthesis, crystal structure, and physical characterization of the coordination compounds [Ni(en)2]4[Fe(CN)5NO]2[Fe(CN)6]x5H2O (1), [Ni(en)2][Fe(CN)5NO]x3H2O (2), [Mn(3-MeOsalen)(H2O)]2[Fe(CN)5NO] (3), and [Mn(5-Brsalen)]2[Fe(CN)5NO] (4) are presented. 1 crystallizes in the monoclinic space group P2(1)/n (a = 7.407(4) A, b = 28.963(6) A, c = 14.744(5) A, alpha = 90 degrees, beta = 103.26(4) degrees, gamma = 90 degrees, Z = 2). Its structure consists of branched linear chains formed by cis-[Ni(en)2]2+ cations and ferrocyanide and nitroprusside anions. The presence of two kinds of iron(II) sites has been demonstrated by M?ssbauer spectroscopy. 2 crystallizes in the monoclinic space group P2(1)/c (a = 11.076(3) A, b = 10.983(2) A, c = 17.018(5) A, alpha = 90 degrees, beta = 107.25(2) degrees, gamma = 90 degrees, Z = 4). Its structure consists of zigzag chains formed by an alternated array of cis-[Ni(en)2]2+ cations and nitroprusside anions. 3 crystallizes in the triclinic space group P1 (a = 8.896(5) A, b = 10.430(5) A, c = 12.699(5) A, alpha = 71.110(5) degrees, beta = 79.990(5) degrees, gamma = 89.470(5) degrees, Z = 1). Its structure comprises neutral trinuclear bimetallic complexes in which a central [Fe(CN)5NO]2- anion is linked to two [Mn(3-MeOsalen)]+ cations. 4 crystallizes in the tetragonal space group P4/ncc (a = 13.630(5) A, c = 21.420(8) A, Z = 4). Its structure shows an extended 2D neutral network formed by cyclic octameric [-Mn-NC-Fe-CN-]4 units. The magnetic properties of these compounds indicate the presence of quasi-isolated paramagnetic Ni2+ and Mn3+. Irradiated samples of the four compounds have been studied by differential scanning calorimetry to detect the existence of the long-lived metastable states of nitroprusside.     

Insertion reactions of [M(SR)3(PMe2Ph)2] with CS2 (M = Ru, Os; R = C6F4H-4, C6F5). X-ray structures of [Ru(S2CSC6F4H-4)2(PMe2Ph)2], trans-thiolates [M(SR)2(S2CSR)(PMe2Ph)2] (M = Ru; R = C6F5 and M = Os; R = C6F4H-4), and trans-thiolate-phosphine [Os(SC6F5)2(S2CSC6F5)(PMe2Ph)2

Reactions of [M(SR)(3)(PMe(2)Ph)(2)] (M = Ru, Os; R = C(6)F(4)H-4, C(6)F(5)) with CS(2) in acetone afford [Ru(S(2)CSR)(2)(PMe(2)Ph)(2)] (R = C(6)F(4)H-4, 1; C(6)F(5), 3) and trans-thiolates [Ru(SR)(2)(S(2)CSR)(PMe(2)Ph)(2)] (R = C(6)F(4)H-4, 2; C(6)F(5), 4) or the isomers trans-thiolates [Os(SR)(2)(S(2)CSR)(PMe(2)Ph)(2)] (R = C(6)F(4)H-4, 5; C(6)F(5), 7) and trans-thiolate-phosphine [Os(SR)(2)(S(2)CSR)(PMe(2)Ph)(2)] (R = C(6)F(4)H-4, 6; C(6)F(5), 8) through processes involving CS(2) insertion into M-SR bonds. The ruthenium(III) complexes [Ru(SR)(3)(PMe(2)Ph)(2)] react with CS(2) to give the diamagnetic thiolate-thioxanthato ruthenium(II) and the paramagnetic ruthenium(III) complexes while osmium(III) complexes [Os(SR)(3)(PMe(2)Ph)(2)] react to give the paramagnetic thiolate-thioxanthato osmium(III) isomers. The single-crystal X-ray diffraction studies of 1, 4, 5, and 8 show distorted octahedral structures. (31)P [(1)H] and (19)F NMR studies show that the solution structures of 1 and 3 are consistent with the solid-state structure of 1.