Hydrothermal Syntheses and Structural Characterization of Layered Vanadium Oxides Incorporating Organic Cations: alpha-, beta-(H(3)N(CH(2))(2)NH(3))[V(4)O(10)] and alpha-, beta-(H(2)N(C(2)H(4))(2)NH(2))[V(4)O(10)

Four new layered mixed-valence vanadium oxides, which contain interlamellar organic cations, alpha-(H(3)N(CH(2))(2)NH(3))[V(4)O(10)] (1a), beta-(H(3)N(CH(2))(2)NH(3))[V(4)O(10)] (1b), alpha-(H(2)N(C(2)H(4))(2)NH(2))[V(4)O(10)] (2a), and beta-(H(2)N(C(2)H(4))(2)NH(2))[V(4)O(10)] (2b), have been prepared under hydrothermal conditions and their single-crystal structures determined: 1a, triclinic, space group P&onemacr;, a = 6.602(2) ?, b = 7.638(2) ?, c = 5.984(2) ?, alpha = 109.55(3) degrees, beta = 104.749(2) degrees, gamma = 82.31(3) degrees, Z = 1; 1b, triclinic, P&onemacr;, a = 6.387(1) ?, b = 7.456(2) ?, c = 6.244(2) ?, alpha = 99.89(2) degrees, beta = 102.91(2) degrees, gamma = 78.74(2) degrees, Z = 1; 2a, triclinic, P&onemacr;, a = 6.3958(5) ?, b = 8.182(1) ?, c = 6.3715(7) ?, alpha = 105.913(9) degrees, beta = 104.030(8) degrees, gamma = 94.495(8) degrees, Z = 1; 2b, monoclinic, space group P2(1)/n, a = 9.360(2) ?, b = 6.425(3) ?, c = 10.391(2) ?, beta = 105.83(1) degrees, Z = 2. All four of the compounds contain mixed-valence V(5+)/V(4+) vanadium oxide layers constructed from V(5+)O(4) tetrahedra and pairs of edge-sharing V(4+)O(5) square pyramids with protonated organic amines occupying the interlayer space.     

Synthesis and Structures of Sb[N(H)(C(6)H(2)(t)Bu(3))](3) and Bi[N(H)(C(6)H(2)(t)Bu(3))](3): Implications for the Steric Limits of Supermesityl Substitution

Syntheses and isolations of the tris(amino)stibine and tris(amino)bismuthine E[N(H)(C(6)H(2)(t)Bu(3))](3) (E = Sb, Bi) from ECl(3) and LiN(H)(C(6)H(2)(t)Bu(3)) are described, together with spectroscopic and structural characterization [crystal data for C(54)H(90)N(3)Sb, M = 903.04, space group P&onemacr;, a = 11.491(5) ?, b = 24.652(7) ?, c = 10.002(5) ?, alpha = 98.38(3) degrees, beta = 96.44(5) degrees, gamma = 77.25(3) degrees, V = 2724(2) ?(3), D(c) = 1.101 Mg/m(3), Z = 2, R = 0.0547; crystal data for C(54)H(90)BiN(3), M = 990.27, space group P&onemacr;, a = 11.511(5) ?, b = 24.785(15) ?, c = 9.981(5) ?, alpha = 98.06(5) degrees, beta = 96.50(4) degrees, gamma = 77.40(5) degrees, V = 2742(2) ?(3), D(c) = 1.200 Mg/m(3), Z = 2, R = 0.0619]. The compounds bear the "bulky" 2,4,6-tri-tert-butylphenyl substituent (known as supermesityl or Mes), and their formation is considered in the context of the same reactions for PCl(3) and AsCl(3), which have been previously shown to produce the aminoiminopnictine structures [N(H)(C(6)H(2)(t)Bu(3))]P=N(C(6)H(2)(t)Bu(3)) and [N(H)(C(6)H(2)(t)Bu(3))]As=N(C(6)H(2)(t)Bu(3)). The observations establish the limits of the steric control by the supermesityl substituent and provide qualitative support for the thermodynamic significance of substituent steric strain.     

Polyfluorinated Tris(pyrazolyl)borates. Syntheses and Spectroscopic and Structural Characterization of Group 1 and Group 11 Metal Complexes of [HB(3,5-(CF(3))(2)Pz)(3)](-) and [HB(3-(CF(3))Pz)(3)](-)

The fluorinated tris(pyrazolyl)borate ligands [HB(3,5-(CF(3))(2)Pz)(3)](-) and [HB(3-(CF(3))Pz)(3)](-) (where Pz = pyrazolyl) have been synthesized as their sodium salts from the corresponding pyrazoles and NaBH(4) in high yield. These sodium complexes and the related [HB(3,5-(CF(3))(2)Pz)(3)]K(DMAC) were used as ligand transfer agents in the preparation of the copper and silver complexes [HB(3,5-(CF(3))(2)Pz)(3)]Cu(DMAC), [HB(3,5-(CF(3))(2)Pz)(3)]CuPPh(3), [HB(3,5-(CF(3))(2)Pz)(3)]AgPPh(3), and [HB(3-(CF(3))Pz)(3)]AgPPh(3). Metal complexes of the fluorinated [HB(3,5-(CF(3))(2)Pz)(3)](-) ligand have highly electrophilic metal sites relative to their hydrocarbon analogs. This is evident from the formation of stable adducts with neutral oxygen donors such as H(2)O, dimethylacetamide, or thf. Furthermore, the metal compounds derived from fluorinated ligands show fairly long-range coupling between fluorines of the trifluoromethyl groups and the hydrogen, silver, or phosphorus. The solid state structures show that the fluorines are in close proximity to these nuclei, thus suggesting a possible through-space coupling mechanism. Crystal structures of the sodium adducts exhibit significant metal-fluorine interactions. The treatment of [HB(3,5-(CF(3))(2)Pz)(3)]Na(H(2)O) with Et(4)NBr led to [Et(4)N][HB(3,5-(CF(3))(2)Pz)(3)], which contains a well-separated [Et(4)N](+) cation and the [HB(3,5-(CF(3))(2)Pz)(3)](-) anion in the solid state. Crystal data with Mo Kalpha (lambda = 0.710 73 ?) at 193 K: [HB(3,5-(CF(3))(2)Pz)(3)]Na(H(2)O), C(15)H(6)BF(18)N(6)NaO, a = 7.992(2) ?, b = 15.049(2) ?, c = 9.934(2) ?, beta = 101.16(2) degrees, monoclinic, P2(1)/m, Z = 2; [{HB(3-(CF(3))Pz)(3)}Na(thf)](2), C(32)H(30)B(2)F(18)N(12)Na(2)O(2), a = 9.063(3) ?, b = 10.183(2) ?, c = 12.129(2) ?, alpha = 94.61(1) degrees, beta = 101.16(2) degrees, gamma = 95.66(2) degrees, triclinic, &Pmacr;1, Z = 1; [HB(3,5-(CF(3))(2)Pz)(3)]Cu(DMAC), C(19)H(13)BCuF(18)N(7)O, a = 15.124(4) ?, b = 8.833(2) ?, c = 21.637(6) ?, beta = 105.291(14) degrees, monoclinic, P2(1)/n, Z = 4; [HB(3,5-(CF(3))(2)Pz)(3)]CuPPh(3), C(33)H(19)BCuF(18)N(6)P, a = 9.1671(8) ?, b = 14.908(2) ?, c = 26.764(3) ?, beta = 94.891(1) degrees, monoclinic, P2(1)/c, Z = 4; [HB(3,5-(CF(3))(2)Pz)(3)]AgPPh(3).0.5C(6)H(14), C(36)H(26)AgBF(18)N(6)P, a = 13.929(2) ?, b = 16.498(2) ?, c = 18.752(2) ?, beta = 111.439(6) degrees, monoclinic, P2(1)/c, Z = 4; [Et(4)N][HB(3,5-(CF(3))(2)Pz)(3)], C(23)H(24)BF(18)N(7), a = 10.155(2) ?, b = 18.580(4) ?, c = 16.875(5) ?, beta = 99.01(2) degrees, monoclinic, P2(1)/n, Z = 4.     

Synthesis, Structure, and Reactivity of [Zr(6)Cl(18)H(5)](2)(-), the First Paramagnetic Species of Its Class

Reaction of [Zr(6)Cl(18)H(5)](3)(-) (1) with 1 equiv of TiCl(4) yields a new cluster anion, [Zr(6)Cl(18)H(5)](2)(-) (2), which can be converted back into [Zr(6)Cl(18)H(5)](3)(-) (1) upon addition of 1 equiv of Na/Hg. Cluster 2 is paramagnetic and unstable in the presence of donor molecules. It undergoes a disproportionation reaction to form 1, some Zr(IV) compounds, and H(2). It also reacts with TiCl(4) to form [Zr(2)Cl(9)](-) (4) and a tetranuclear mixed-metal species, [Zr(2)Ti(2)Cl(16)](2)(-) (3). The oxidation reaction of 1 with TiCl(4) is unique. Oxidation of 1 with H(+) in CH(2)Cl(2) solution results in the formation of [ZrCl(6)](2)(-) (5) and H(2), while in py solution the oxidation product is [ZrCl(5)(py)](-) (6). There is no reaction between 1 and TiI(4), ZrCl(4), [TiCl(6)](2)(-), [ZrCl(6)](2)(-), or CrCl(3). Compounds [Ph(4)P](2)[Zr(6)Cl(18)H(5)] (2a), [Ph(4)P](2)[Zr(2)Ti(2)Cl(16)] (3a), [Ph(4)P](2)[Zr(2)Cl(9)] (4a), [Ph(4)P](2)[ZrCl(6)].4MeCN (5a.4MeCN), and [Ph(4)P][ZrCl(5)(py)] (6a) were characterized by X-ray crystallography. Compound 2a crystallized in the trigonal space group R&thremacr; with cell dimensions (20 degrees C) of a = 28.546(3) ?, b = 28.546(3) ?, c = 27.679(2) ?, V = 19533(3) ?(3), and Z = 12. Compound 3a crystallized in the triclinic space group P&onemacr; with cell dimensions (-60 degrees C) of a = 11.375(3) ?, b = 13.357(3) ?, c = 11.336(3) ?, alpha = 106.07(1) degrees, beta = 114.77(1) degrees, gamma = 88.50(1) degrees, V = 1494.8(7) ?(3), and Z = 1. Compound 4a crystallized in the triclinic space group P&onemacr; with cell dimensions (-60 degrees C) of a = 12.380(5) ?, b = 12.883(5) ?, c = 11.000(4) ?, alpha = 110.39(7) degrees, beta = 98.29(7) degrees, gamma = 73.12(4) degrees, V = 1572(1) ?(3), and Z = 2. Compound 5a.4MeCN crystallized in the monoclinic space group P2(1)/c with cell dimensions (-60 degrees C) of a = 9.595(1) ?, b = 19.566(3) ?, c = 15.049(1) ?, beta = 98.50(1) degrees, V = 2794.2(6) ?(3), and Z = 2. Compound 6a crystallized in the monoclinic space group P2(1)/c with cell dimensions (20 degrees C) of a = 10.3390(7) ?, b = 16.491(2) ?, c = 17.654(2) ?, beta = 91.542(6) degrees, V = 3026.4(5) ?(3), and Z = 4.     

An Approach to Heterometallic Complexes with Selenolate and Tellurolate Ligands: Crystal Structures of cis-[Mn(CO)(4)(SePh)(2)](-), [(CO)(3)Mn(&mgr;-SeMe)(3)Mn(CO)(3)](-), (CO)(4)Mn(&mgr;-TePh)(2)Co(CO)(&mgr;-SePh)(3)Mn(CO)(3), and (CO)(3)Mn(&mgr;-SePh)(3)Fe(CO)(3)

Oxidative addition of diorganyl diselenides to the coordinatively unsaturated, low-valent transition-metal-carbonyl fragment [Mn(CO)(5)](-) produced cis-[Mn(CO)(4)(SeR)(2)](-). The complex cis-[PPN][Mn(CO)(4)(SePh)(2)] crystallized in triclinic space group P&onemacr; with a = 10.892(8) ?, b = 10.992(7) ?, c = 27.021(4) ?, alpha = 101.93(4) degrees, beta = 89.79(5) degrees, gamma = 116.94(5) degrees, V = 2807(3) ?(3), and Z = 2; final R = 0.085 and R(w) = 0.094. Thermolytic transformation of cis-[Mn(CO)(4)(SeMe)(2)](-) to [(CO)(3)Mn(&mgr;-SeMe)(3)Mn(CO)(3)](-) was accomplished in high yield in THF at room temperature. Crystal data for [Na-18-crown-6-ether][(CO)(3)Mn(&mgr;-SeMe)(3)Mn(CO)(3)]: trigonal space group R&thremacr;, a = 13.533(3) ?, c = 32.292(8) ?, V = 5122(2) ?(3), Z = 6, R = 0.042, R(w) = 0.041. Oxidation of Co(2+) to Co(3+) by diphenyl diselenide in the presence of chelating metallo ligands cis-[Mn(CO)(4)(SePh)(2)](-) and cis-[Mn(CO)(4)(TePh)(2)](-), followed by a bezenselenolate ligand rearranging to bridge two metals and a labile carbonyl shift from Mn to Co, led directly to [(CO)(4)Mn(&mgr;-TePh)(2)Co(CO)(&mgr;-SePh)(3)Mn(CO)(3)]. Crystal data: triclinic space group P&onemacr;, a = 11.712(3) ?, b = 12.197(3) ?, c = 15.754(3) ?, alpha = 83.56(2) degrees, beta = 76.13(2) degrees, gamma = 72.69(2) degrees, V = 2083.8(7) ?(3), Z = 2, R = 0.040, R(w) = 0.040. Addition of fac-[Fe(CO)(3)(SePh)(3)](-) to fac-[Mn(CO)(3)(CH(3)CN)(3)](+) resulted in formation of (CO)(3)Mn(&mgr;-SePh)(3)Fe(CO)(3). This neutral heterometallic complex crystallized in monoclinic space group P2(1)/n with a = 8.707(2) ?, b = 17.413(4) ?, c = 17.541(4) ?, beta = 99.72(2) degrees, V = 2621(1) ?(3), and Z = 4; final R = 0.033 and R(w) = 0.030.     

Pyridineselenolate Complexes of Copper and Indium: Precursors to CuSe(x)() and In(2)Se(3)

The pyridineselenolate (2-Se-NC(5)H(4), (SePy)) and the 3-(trimethylsilyl)pyridineselenolate (3-Me(3)Si-2-Se-NC(5)H(4) (SePy)) ligands form air-stable homoleptic coordination compounds of Cu(I) { [Cu(SePy)](4) (1) and [Cu(SePy)](4) (2)} and In(III) {In(SePy)(3) (3) and In(SePy)(3) (4)}. Mass spectroscopic characterization of the Cu(I) compounds indicated a tetrametallic core, and this was confirmed with a single-crystal X-ray structural characterization of crystalline 1 and 2, which both contain a tetrametallic cluster of Cu(I) ions bound to two doubly bridging Se atoms and a pyridine nitrogen. The Cu coordination sphere is completed with two strong Cu-Cu bonds and one weaker Cu-Cu interaction. The indium compounds 3 and 4 are each distorted fac-octahedral molecules with chelating SePy ligands. These compounds are useful low-temperature precursors to the binary selenides. Both 3 and 4 sublime intact; 3 thermally decomposes to give In(2)Se(3). The Cu clusters do not sublime intact but still decompose to give metal selenide phases: 2 decomposes to give pure alpha-CuSe at low temperatures and increasing amounts of Cu(2)(-)(x)()Se at elevated temperatures, while 3 decomposes to give a mixture of CuSe phases at all temperatures. Crystal data (Mo Kalpha: 1, 153(5) K; 2-4, 293(2) K) are as follows: 1, monoclinic space group C2/c, a = 20.643(5) ?, b = 16.967(2) ?, c = 16.025(2) ?, beta = 114.16(2) degrees, Z = 8; 2, tetragonal space group I4(1)/a, a = 14.756(3) ?, c = 19.925(3) ?, Z = 4; 3, trigonal space group P&thremacr;c1, a = 13.352(2) ?, c = 13.526(2) ?, Z = 4; 4, monoclinic space group P2(1)/c, a = 9.793(1) ?, b = 20.828(6) ?, c = 16.505(1) ?, beta = 96.69(1) degrees, Z = 4.     

Copper and Bismuth Complexes Containing Dipyridyl gem-Diolato Ligands: Bi(III)(2)[(2-Py)(2)CO(OH)](2)(O(2)CCF(3))(4)(THF)(2), Cu(II)[(2-Py)(2)CO(OH)](2)(HO(2)CCH(3))(2), and Cu(II)(4)[(2-Py)(2)CO(OH)](2)(O(2)CCH(3))(6)(H(2)O)(2), a Ferromagnetically Coupled Tetranuclear Copper(II) Chain

The reactions of the singly deprotonated di-2-pyridylmethanediol ligand (dpmdH(-)) with copper(II) and bismuth(III) have been investigated. A new dinuclear bismuth(III) complex Bi(2)(dpmdH)(2)(O(2)CCF(3))(4)(THF)(2), 1, has been obtained by the reaction of BiPh(3) with di-2-pyridyl ketone in the presence of HO(2)CCF(3) in tetrahydrofuran (THF). The reaction of Cu(OCH(3))(2) with di-2-pyridyl ketone, H(2)O, and acetic acid in a 1:2:2:2 ratio yielded a mononuclear complex Cu[(2-Py)(2)CO(OH)](2)(HO(2)CCH(3))(2), 2, while the reaction of Cu(OAC)(2)(H(2)O) with di-2-pyridyl ketone and acetic acid in a 2:1:1 ratio yielded a tetranuclear complex Cu(4)[(2-Py)(2)CO(OH)](2)(O(2)CCH(3))(6)(H(2)O)(2), 3. The structures of these complexes were determined by single-crystal X-ray diffraction analyses. Three different bonding modes of the dpmdH(-) ligand were observed in compounds 1-3. In 2, the dpmdH(-) ligand functions as a tridentate chelate to the copper center and forms a hydrogen bond between the OH group and the noncoordinating HO(2)CCH(3) molecule. In 1 and 3, the dpmdH(-) ligand functions as a bridging ligand to two metal centers through the oxygen atom. The two pyridyl groups of the dpmdH(-) ligand are bound to one bismuth(III) center in 1, while in 3 they are bound two copper(II) centers, respectively. Compound 3 has an unusual one dimensional hydrogen bonded extended structure. The intramolecular magnetic interaction in 3 has been found to be dominated by ferromagnetism. Crystal data: 1, C(38)H(34)N(4)O(14)F(12)Bi(2), triclinic P&onemacr;, a = 11.764(3) ?, b = 11.949(3) ?, c = 9.737(1) ?, alpha =101.36(2) degrees, beta = 105.64(2) degrees, gamma = 63.79(2) degrees, Z = 1; 2, C(26)H(26)N(4)O(8)Cu/CH(2)Cl(2), monoclinic C2/c, a = 25.51(3) ?, b = 7.861(7) ?, c = 16.24(2) ?, beta = 113.08(9) degrees, Z = 4; 3, C(34)H(40)N(4)O(18)Cu(4)/CH(2)Cl(2), triclinic P&onemacr;, a = 10.494(2) ?, b = 13.885(2) ?, c = 7.900(4) ?, alpha =106.52(2) degrees, beta = 90.85(3) degrees, gamma = 94.12(1) degrees, Z = 1.     

Syntheses,reactivity, and crystal structures of molybdenum complexes with pyridine-2-thionate (pyS)-containing ligands: crystal structures of [Mo(eta(3)-C(3)H(5))(CO)(2)](2)(mu-eta(1),eta(2)-pyS)(2), exo-[Mo(eta(3)-C(3)H(5))(CO)(eta(2)-pyS)(eta(2)-dppe)], [Mo(CO)(3)(eta(1)-SC(5)H(4)NH)(eta(2)-dppm)], and [Mo(CO)(eta(2)-pyS)(2)(eta(2)-dppm)

The doubly bridged pyridine-2-thionate (pyS) dimolybdenum complex [Mo(eta(3)-C(3)H(5))(CO)(2)](2)(mu-eta(1),eta(2)-pyS)(2) (1) is accessible by the reaction of [Mo(eta(3)-C(3)H(5))(CO)(2)(CH(3)CN)(2)Br] with pySK in methanol at room temperature. Complex 1 reacts with piperidine in acetonitrile to give the complex [Mo(eta(3)-C(3)H(5))(CO)(2)(eta(2)-pyS)(C(5)H(10)NH)] (2). Treatment of 1 with 1,10-phenanthroline (phen) results in the formation of complex [Mo(eta(3)-C(3)H(5))(CO)(2)(eta(1)-pyS)(phen)] (3), in which the pyS ligand is coordinated to Mo through the sulfur atom. Four conformational isomers, endo,exo-complexes [Mo(eta(3)-C(3)H(5))(CO)(eta(2)-pyS)(eta(2)-diphos)] (diphos = dppm, 4a-4d; dppe, 5a-5d), are accessible by the reactions of 1 with dppm and dppe in refluxing acetonitrile. Homonuclear shift-correlated 2-D (31)P((1)H)-(31)P((1)H) NMR experiments of the mixtures 4a-4d have been employed to elucidate the four stereoisomers. The reaction of 4 and pySK or [Mo(CO)(3)(eta(1)-SC(5)H(4)NH)(eta(2)-dppm)] (6) and O(2) affords allyl-displaced seven-coordinate bis(pyridine-2-thionate) complex [Mo(CO)(eta(2)-pyS)(2)(eta(2)-dppm)] (7). All of the complexes are identified by spectroscopic methods, and complexes 1, 5d, 6, and 7 are determined by single-crystal X-ray diffraction. Complexes 1 and 5d crystallize in the orthorhombic space groups Pbcn and Pbca with Z = 4 and 8, respectively, whereas 6 belongs to the monoclinic space group C2/c with Z = 8 and 7 belongs to the triclinic space group Ponemacr; with Z = 2. The cell dimensions are as follows: for 1, a = 8.3128(1) A, b = 16.1704(2) A, c = 16.6140(2) A; for 5d, a = 17.8309(10) A, b = 17.3324(10) A, c = 20.3716(11) A; for 6, a = 18.618(4) A, b = 16.062(2) A, c = 27.456(6) A, beta = 96.31(3) degrees; for 7, a = 9.1660(2) A, b = 12.0854(3) A, c = 15.9478(4) A, alpha = 78.4811(10) degrees, beta = 80.3894(10) degrees, gamma = 68.7089(11) degrees.     

Synthesis, Structure, and Reactivities of [eta(2)-P(7)M(CO)(4)](3)(-), [eta(2)-HP(7)M(CO)(4)](2)(-), and [eta(2)-RP(7)M(CO)(4)](2)(-) Zintl Ion Complexes Where M = Mo, W

Ethylenediamine (en) solutions of [eta(4)-P(7)M(CO)(3)](3)(-) ions [M = W (1a), Mo (1b)] react under one atmosphere of CO to form microcrystalline yellow powders of [eta(2)-P(7)M(CO)(4)](3)(-) complexes [M = W (4a), Mo (4b)]. Compounds 4 are unstable, losing CO to re-form 1, but are highly nucleophilic and basic. They are protonated with methanol in en solvent giving [eta(2)-HP(7)M(CO)(4)](2)(-) ions (5) and are alkylated with R(4)N(+) salts in en solutions to give [eta(2)-RP(7)M(CO)(4)](2)(-) complexes (6) in good yields (R = alkyl). Compounds 5 and 6 can also be prepared by carbonylations of the [eta(4)-HP(7)M(CO)(3)](2)(-) (3) and [eta(4)-RP(7)M(CO)(3)](2)(-) (2) precursors, respectively. The carbonylations of 1-3 to form 4-6 require a change from eta(4)- to eta(2)-coordination of the P(7) cages in order to maintain 18-electron configurations at the metal centers. Comparative protonation/deprotonation studies show 4 to be more basic than 1. The compounds were characterized by IR and (1)H, (13)C, and (31)P NMR spectroscopic studies and microanalysis where appropriate. The [K(2,2,2-crypt)](+) salts of 5 were characterized by single crystal X-ray diffraction. For 5, the M-P bonds are very long (2.71(1) ?, average). The P(7)(3)(-) cages of 5 are not displaced by dppe. The P(7) cages in 4-6 have nortricyclane-like structures in contrast to the norbornadiene-type geometries observed for 1-3. (31)P NMR spectroscopic studies for 5-6 show C(1) symmetry in solution (seven inequivalent phosphorus nuclei), consistent with the structural studies for 5, and C(s)() symmetry for 4 (five phosphorus nuclei in a 2:2:1:1:1 ratio). Crystallographic data for [K(2,2,2-crypt)](2)[eta(2)-HP(7)W(CO)(4)].en: monoclinic, space group C2/c, a = 23.067(20) ?, b = 12.6931(13) ?, c = 21.433(2) ?, beta = 90.758(7) degrees, V = 6274.9(10) ?(3), Z = 4, R(F) = 0.0573, R(w)(F(2)) = 0.1409. For [K(2,2,2-crypt)](2)[eta(2)-HP(7)Mo(CO)(4)].en: monoclinic, space group C2/c, a = 22.848(2) ?, b = 12.528(2) ?, c = 21.460(2) ?, beta = 91.412(12) degrees, V = 6140.9(12) ?(3), Z = 4, R(F) = 0.0681, R(w)(F(2)) = 0.1399.     

Experimental and Theoretical Investigations of the Formation of the Diazene PhSN=C(H)N=NC(H)=NSPh from HCN(2)(SPh)(3) by a Thiyl-Radical-Catalyzed Mechanism: Identification of the HC(NSPh)(2)(*) Radical and X-ray Structures of HCN(2)(SPh)(3) and PhSN=C(H)N=NC(H)=NSPh

The reaction of HCN(2)(SiMe(3))(3) with benzenesulfenyl chloride in a 1:3 molar ratio produces HCN(2)(SPh)(3) (4) as thermally unstable, colorless crystals. The decomposition of (4) in toluene at 95 degrees C was monitored by UV-visible, (1)H NMR and ESR spectroscopy. The major final products of the decomposition were identified as PhSN=C(H)N=NC(H)=NSPh (5) and PhSSPh. The structures of 4 and 5 were determined by X-ray crystallography. The crystals of 4 are monoclinic, space group P2(1)/a, with a = 9.874(2) ?, b = 19.133(2) ?, c = 10.280(2) ?, beta = 113.37(1) degrees, V = 1782.8(5) ?(3), and Z = 4. The final R and R(w) values were 0.042 and 0.049, respectively. The crystals of 5 are monoclinic, space group P2(1)/n, with a = 5.897(6) ?, b = 18.458(10) ?, c = 7.050(8) ?, beta = 110.97(5) degrees, V = 716(1) ?(3), and Z = 2. The final R and R(w) values were 0.075 and 0.085, respectively. The diazene 5 adopts a Z,E,Z structure with weak intramolecular S.N contacts of 2.83 ?, giving rise to four-membered NCNS rings. During the thermolysis of 4 at 95 degrees C in toluene a transient species (lambda(max) 820 nm) was detected. It decomposes with second-order kinetics to give 5 (lambda(max) 450 nm). The ESR spectrum of the reaction mixture consisted of the superposition of a three-line 1:1:1 spectrum (g = 2.0074, A(N) = 11.45 G), attributed to (PhS)(2)N(*), upon a doublet of quintets (1:2:3:2:1) with g = 2.0070, A(N) = 6.14 G, A(H) = 2.1 G assigned to the radical HCN(2)(SPh)(2)(*). Density functional theory (DFT) calculations for the models of the radical showed the E,Z isomer to have the lowest energy. Thermochemical calculations indicate that the decomposition of HCN(2)(SH)(3) into the diazene (Z,E,Z)-HSN=C(H)N=NC(H)=NSH (and 2 HSSH) is substantially more exothermic (DeltaH = -176.1 kJ mol(-)(1)) than the corresponding formation of the isomeric eight-membered ring (HC)(2)N(4)(SH)(2) (DeltaH = -40.6 kJ mol(-)(1)). These calculations also indicate that the diazene is formed by a mechanism in which the RS(*) radical acts as a catalyst.     

Aluminum Amides Derived from Metalation of N,N'-Bis(trimethylsilyl)ethylenediamine

The reaction of N,N'-bis(trimethylsilyl)ethylenediamine with H(3)Al.NMe(3) gives products based on metalation (H(2) elimination), [{[CH(2)N(SiMe(3))](2)AlH}(2)] (1) and [{CH(2)N(SiMe(3))}(2)AlN(SiMe(3))CH(2)CH(2)N(H)SiMe(3)] (2), as well as products derived from N-Si bond cleavage and metalation, [{[CH(2)N(SiMe(3))](2)AlH}(2){HAlN(SiMe(3))CH(2)CH(2)NAlH(2)}] (4) and [H(2)Al{CH(2)N(SiMe(3))}(2)AlN(SiMe(3))CH(2)CH(2)NAl(H)(2).NMe(3)}] (5). Similarly, [Me(3)SiN(H)CH(2)CH(2)N(SiMe(3))AlCl(2)] (3) was isolated as the redistributed/metalated product from the reaction of the same diamine with H(2)Al(Cl).NMe(3). The following crystal data were obtained: (1) monoclinic, space group P2(1)/c (No. 14), a = 13.636(4) ?, b = 9.565(3) ?, c = 22.683(4) ?, beta = 105.67(2) degrees, Z = 4; (2) monoclinic, space group C2/c (No. 15), a = 31.887(3) ?, b = 10.145(6) ?, c = 17.718(3) ?, beta = 100.36(1) degrees, Z = 8; (3) triclinic, space group P&onemacr; (No. 2), a = 11.762(3) ?, b = 11.927(3) ?, c = 7.288(2) ?, alpha = 107.46(2) degrees, beta = 95.29(2) degrees, gamma = 110.41(2) degrees, Z = 2; (4) triclinic, space group P&onemacr; (No. 2), a = 13.884(4) ?, b = 15.379(4) ?, c = 11.044(2) ?, alpha = 102.11(2) degrees, beta = 103.85(2) degrees, gamma = 109.28(2) degrees, Z = 2; (5) triclinic, space group P&onemacr; (No. 2), a = 10.925(5) ?, b = 11.060(5) ?, c = 12.726(4) ?, alpha = 92.38(3) degrees, beta = 95.67(2) degrees, gamma = 96.90(2) degrees, Z = 2.     

Synthesis, Characterization, and Comparative Properties of [PPN](2)[Re(6)C(CO)(18)Mo(CO)(4)] and [PPN](2)[Re(6)C(CO)(18)Ru(CO)(3)

The reaction of [PPN](2)[Re(6)C(CO)(19)] with Mo(CO)(6) and Ru(3)(CO)(12) under sunlamp irradiation provided the new mixed-metal clusters [PPN](2)[Re(6)C(CO)(18)Mo(CO)(4)] and [PPN](2)[Re(6)C(CO)(18)Ru(CO)(3)], which were isolated in yields of 85% and 61%, respectively. The compound [PPN](2)[Re(6)C(CO)(18)Mo(CO)(4)] crystallizes in the monoclinic space group P2(1)/c with a = 20.190 (7) ?, b = 16.489 (7) ?, c = 27.778 (7) ?, beta = 101.48 (2) degrees, and Z = 4 (at T = -75 degrees C). The cluster anion is composed of a Re(6)C octahedral core with a face capped by a Mo(CO)(4) fragment. There are three terminal carbonyl ligands coordinated to each rhenium atom. The four carbonyl ligands on the molybdenum center are essentially terminal, with one pair of carbonyl ligands (C72-O72 and C74-O74) subtending a relatively large angle at molybdenum (C72-Mo-C74 = 147.2(9) degrees ), whereas the remaining pair of carbonyl ligands (C71-O71 and C73-O73) subtend a much smaller angle (C71-Mo-C73 = 100.5(9) degrees ). The (13)C NMR spectrum of (13)CO-enriched [PPN](2)[Re(6)C(CO)(18)Mo(CO)(4)] shows signals for four sets of carbonyl ligands at -40 degrees C, consistent with the solid state structure, but the carbonyl ligands undergo complete scrambling at ambient temperature. The (13)C NMR spectrum of (13)CO-enriched [PPN](2)[Re(6)C(CO)(18)Ru(CO)(3)] at 20 degrees C is consistent with the expected structure of an octahedral Re(6)C(CO)(18) core capped by a Ru(CO)(3) fragment. The visible spectrum of [PPN](2)[Re(6)C(CO)(18)Mo(CO)(4)] shows a broad, strong band at 670 nm (epsilon = 8100), whereas all of the absorptions of [PPN](2)[Re(6)C(CO)(18)Ru(CO)(3)] are at higher energy. An irreversible oxidation wave with E(p) at 0.34 V is observed for [PPN](2)[Re(6)C(CO)(18)Mo(CO)(4)], whereas two quasi-reversible oxidation waves with E(1/2) values of 0.21 and 0.61 V (vs Ag/AgCl) are observed for [PPN](2)[Re(6)C(CO)(18)Ru(CO)(3)]. The molybdenum cap in [Re(6)C(CO)(18)Mo(CO(4))](2-) is cleaved by heating in donor solvents, and by treatment with H(2), to give largely [H(2)Re(6)C(CO)(18)](2-). In contrast, [Re(6)C(CO)(18)Ru(CO)(3)](2-) shows no tendency to react under similar conditions.     

Ruthenium Complexes Containing "Noninnocent" o-Benzoquinone Diimine/o-Phenylenediamide(2-) Ligands. Synthesis and Crystal Structure of the Nitrido-Bridged Complex [{LRu(o-C(6)H(4)(NH)(2))}(2)(&mgr;-N)](PF(6))(2).3CH(3)CN.C(6)H(5)CH(3)

Reaction of LRu(III)Cl(3) (L = 1,4,7-trimethyl-1,4,7-triazacyclononane) with 1,2-phenylenediamine (opdaH(2)) in H(2)O in the presence of air affords [LRu(II)(bqdi)(OH(2))](PF(6)) (1), where (bqdi) represents the neutral ligand o-benzoquinone diimine. From an alkaline methanol/water mixture of 1 was obtained the dinuclear species [{LRu(II)(bqdi)}(2)(&mgr;-H(3)O(2))](PF(6))(3) (1a). The coordinated water molecule in 1 is labile and can be readily substituted under appropriate reaction conditions by acetonitrile, yielding [LRu(II)(bqdi)(CH(3)CN)](PF(6))(2) (2), and by iodide and azide anions, affording [LRu(II)(bqdi)I](PF(6)).0.5H(2)O (3) and [LRu(bqdi)(N(3))](PF(6)).H(2)O (4), respectively. Heating of solid 4 in vacuum at 160 degrees C generates N(2) and the dinuclear, nitrido-bridged complex [{LRu(o-C(6)H(4)(NH)(2))}(2)(&mgr;-N)](PF(6))(2) (5). Complex 5 is a mixed-valent, paramagnetic species containing one unpaired electron per dinuclear unit whereas complexes 1-4 are diamagnetic. The crystal structures of 1, 1a.3CH(3)CN, 3, 4.H(2)O, and 5.3CH(3)CN.0.5(toluene) have been determined by X-ray crystallography: 1 crystallizes in the monoclinic space group P2(1)/m, Z = 2, with a = 8.412(2) ?, b = 15.562(3) ?, c = 10.025 ?, and beta = 109.89(2) degrees; 1a.3CH(3)CN, in the monoclinic space group C2/c, Z = 4, with a = 19.858(3) ?, b = 15.483(2) ?, c = 18.192(3) ?, and beta = 95.95(2) degrees; 3, in the orthorhombic space group Pnma, Z = 4, with a = 18.399(4) ?, b = 9.287(2) ?, and c = 12.052(2) ?, 4.H(2)O, in the monoclinic space group P2(1)/c, Z = 4, with a = 8.586(1) ?, b = 15.617(3) ?, c = 16.388(5) ?, and beta = 90.84(2) degrees; and 5.3CH(3)CN.0.5(toluene), in the monoclinic space group P2(1)/c, Z = 4, with a = 15.003(3) ?, b = 16.253(3) ?, c = 21.196(4) ?, and beta = 96.78(3) degrees. The structural data indicate that in complexes 1-4 the neutral o-benzoquinone diimine ligand prevails. In contrast, in 5 this ligand has predominantly o-phenylenediamide character, which would render 5 formally a mixed-valent Ru(IV)Ru(V) species. On the other hand, the Ru-N bond lengths of the Ru-N-Ru moiety at 1.805(5) and 1.767(5) ? are significantly longer than those in other crystallographically characterized Ru(IV)=N=Ru(IV) units (1.72-1.74 ?). It appears that the C(6)H(4)(NH)(2) ligand in 5 is noninnocent and that formal oxidation state assignments to the ligands or metal centers are not possible.     

Unsymmetrical linear pentanuclear nickel string complexes: [Ni(5)(tpda)(4)(H(2)O)(BF(4))](BF(4))(2) and [Ni(5)(tpda)(4)(SO(3)CF(3))(2)](SO(3)CF(3))

The one-electron oxidized linear pentanuclear nickel complexes [Ni(5)(tpda)(4)(H(2)O)(BF(4))](BF(4))(2) (1) and [Ni(5)(tpda)(4)(SO(3)CF(3))(2)](SO(3)CF(3)) (2) have been synthesized by reacting the neutral compound [Ni(5)(tpda)(4)Cl(2)] with the corresponding silver salts. These compounds have been characterized by various spectroscopic techniques. Compound 1 crystallizes in the monoclinic space group P2(1)/n with a = 15.3022(1) A, b = 31.0705(3) A, c = 15.8109(2) A, beta = 92.2425(4) degrees, V = 7511.49(13) A(3), Z = 4, and compound 2 crystallizes in the monoclinic space group C2/c with a = 42.1894(7) A, b = 17.0770(3) A, c = 21.2117(4) A, beta = 102.5688(8) degrees, V = 14916.1(5) A(3), Z = 8. X-ray structural studies reveal an unsymmetrical Ni(5) unit for both compounds 1 and 2. Compounds 1 and 2 show stronger Ni-Ni interactions as compared to those of the neutral compounds.     

Gold(I) Complexes with the nido-Diphosphino Ligand [7,8-(Ph(2)P)(2)-7,8-C(2)B(9)H(10)](-). Preparation of the First Metallocarborane Complex of this Ligand. Crystal Structures of [Au{(PPh(2))(2)C(2)B(9)H(10)}(PPh(3))].CH(2)Cl(2) and [Au(2){(PPh(2))(2)C(2)B(9)H(10)}(2){(PPh(2))(2)(CH(2))(3)}].3Me(2)CO

The reaction of [AuCl(PR(3))] with [1,2-(Ph(2)P)(2)-1,2-C(2)B(10)H(10)] in refluxing ethanol proceeds with partial degradation (removal of a boron atom adjacent to carbon) of the closo species to give [Au{(PPh(2))(2)C(2)B(9)H(10)}(PR(3))] [PR(3) = PPh(3) (1), PPh(2)Me (2), PPh(2)(4-Me-C(6)H(4)) (3), P(4-Me-C(6)H(4))(3) (4), P(4-OMe-C(6)H(4))(3) (5)]. Similarly, the treatment of [Au(2)Cl(2)(&mgr;-P-P)] with [1,2-(Ph(2)P)(2)-1,2-C(2)B(10)H(10)] under the same conditions leads to the complexes [Au(2){(PPh(2))(2)C(2)B(9)H(10)}(2)(&mgr;-P-P)] [P-P = dppe = 1,2-bis(diphenylphosphino)ethane (6), dppp = 1,3-bis(diphenylphosphino)propane (7)], where the dppe or dppp ligands bridge two gold nido-diphosphine units. The reaction of 1 with NaH leads to removal of one proton, and further reaction with [Au(PPh(3))(tht)]ClO(4) gives the novel metallocarborane compound [Au(2){(PPh(2))(2)C(2)B(9)H(9)}(PPh(3))(2)] (8). The structure of complexes 1 and 7 have been established by X-ray diffraction. [Au{(PPh(2))(2)C(2)B(9)H(10)}(PPh(3))] (1) (dichloromethane solvate) crystallizes in the monoclinic space group P2(1)/c, with a = 17.326(3) ?, b = 20.688(3) ?, c = 13.442(2) ?, beta = 104.710(12) degrees, Z = 4, and T = -100 degrees C. [Au(2){(PPh(2))(2)C(2)B(9)H(10)}(2)(&mgr;-dppp)] (7) (acetone solvate) is triclinic, space group P&onemacr;, a = 13.432(3) ?, b = 18.888(3) ?, c = 20.021(3) ?, alpha = 78.56(2) degrees, beta = 72.02(2) degrees, gamma = 73.31(2) degrees, Z = 2, and T = -100 degrees C. In both complexes the gold atom exhibits trigonal planar geometry with the 7,8-bis(diphenylphosphino)-7,8-dicarba-nido-undecaborate(1-) acting as a chelating ligand.     

Mixed-metal uranium(VI) iodates: hydrothermal syntheses,structures, and reactivity of Rb[UO(2)(CrO(4))(IO(3))(H(2)O)], A(2)[UO(2)(CrO(4))(IO(3))(2)] (A = K,Rb, Cs), and K(2)[UO(2)(MoO(4))(IO(3))(2)

The reactions of the molecular transition metal iodates A[CrO(3)(IO(3))] (A = K, Rb, Cs) with UO(3) under mild hydrothermal conditions provide access to four new, one-dimensional, uranyl chromatoiodates, Rb[UO(2)(CrO(4))(IO(3))(H(2)O)] (1) and A(2)[UO(2)(CrO(4))(IO(3))(2)] (A = K (2), Rb (3), Cs (4)). Under basic conditions, MoO(3), UO(3), and KIO(4) can be reacted to form K(2)[UO(2)(MoO(4))(IO(3))(2)] (5), which is isostructural with 2 and 3. The structure of 1 consists of one-dimensional[UO(2)(CrO(4))(IO(3))(H(2)O)](-) ribbons that contain uranyl moieties bound by bridging chromate and iodate anions as well as a terminal water molecule to create [UO(7)] pentagonal bipyramidal environments around the U(VI) centers. These ribbons are separated from one another by Rb(+) cations. When the iodate content is increased in the hydrothermal reactions, the terminal water molecule is replaced by a monodentate iodate anion to yield 2-4. These ribbons can be further modified by replacing tetrahedral chromate anions with MoO(4)(2)(-) anions to yield isostructural, one-dimensional [UO(2)(MoO(4))(IO(3))(2)](2)(-) ribbons. Crystallographic data: 1, triclinic, space group P(-)1, a = 7.3133(5) A, b = 8.0561(6) A, c = 8.4870(6) A, alpha = 88.740(1) degrees, beta = 87.075(1) degrees, gamma = 71.672(1) degrees, Z = 2; 2, monoclinic, space group P2(1)/c, a = 11.1337(5) A, b = 7.2884(4) A, c = 15.5661(7) A, beta = 107.977(1) degrees, Z = 4; 3, monoclinic, space group P2(1)/c, a = 11.3463(6) A, b = 7.3263(4) A, c = 15.9332(8) A, beta = 108.173(1) degrees, Z = 4; 4, monoclinic, space group P2(1)/n, a = 7.3929(5) A, b = 8.1346(6) A, c = 22.126(2) A, beta = 90.647(1) degrees, Z = 4; 5, monoclinic, space group P2(1)/c, a = 11.3717(6) A, b = 7.2903(4) A, c = 15.7122(8) A, beta = 108.167(1) degrees, Z = 4.     

Synthesis, characterization and magnetic properties of four new organically templated metal sulfates [C5H14N2][M(II)(H2O)6](SO4)2, (M(II) = Mn, Fe, Co, Ni)

A series of novel organically templated metal sulfates, [C(5)H(14)N(2)][M(II)(H(2)O)(6)](SO(4))(2) with (M(II) = Mn (1), Fe (2), Co (3) and Ni (4)), have been successfully synthesized by slow evaporation and characterized by single-crystal X-ray diffraction as well as with infrared spectroscopy, thermogravimetric analysis and magnetic measurements. All compounds were prepared using a racemic source of the 2-methylpiperazine and they crystallized in the monoclinic systems, P2(1)/n for (1, 3) and P2(1)/c for (2,4). Crystal data are as follows: [C(5)H(14)N(2)][Mn(H(2)O)(6)](SO(4))(2), a = 6.6385(10) ?, b = 11.0448(2) ?, c = 12.6418(2) ?, β = 101.903(10)°, V = 906.98(3) ?(3), Z = 2; [C(5)H(14)N(2)][Fe(H(2)O)(6)](SO(4))(2), a = 10.9273(2) ?, b = 7.8620(10) ?, c = 11.7845(3) ?, β = 116.733(10)°, V = 904.20(3) ?(3), Z = 2; [C(5)H(14)N(2)][Co(H(2)O)(6)](SO(4))(2), a = 6.5710(2) ?, b = 10.9078(3) ?, c = 12.5518(3) ?, β = 101.547(2)°, V = 881.44(4) ?(3), Z = 2; [C(5)H(14)N(2)][Ni(H(2)O)(6)](SO(4))(2), a = 10.8328(2) ?, b = 7.8443(10) ?, c = 11.6790(2) ?, β = 116.826(10)°, V = 885.63(2) ?(3), Z = 2. The three-dimensional structure networks for these compounds consist of isolated [M(II)(H(2)O)(6)](2+) and [C(5)H(14)N(2)](2+) cations and (SO(4))(2-) anions linked by hydrogen-bonds only. The use of racemic 2-methylpiperazine results in crystallographic disorder of the amines and creation of inversion centers. The magnetic measurements indicate that the Mn complex (1) is paramagnetic, while compounds 2, 3 and 4, (M(II) = Fe, Co, Ni respectively) exhibit single ion anisotropy.     

Reactions of the Dirhenium(II) Complexes Re(2)X(4)(dppm)(2) (X = Cl, Br; dppm = Ph(2)PCH(2)PPh(2)) with Isocyanides. 10.(1) Synthesis and Characterization of the Complex [Re(2)Br(3)(&mgr;-dppm)(2)(CO)(2)(CNXyl)]O(3)SCF(3) and Several Isomeric Forms of [Re(2)Br(3)(&mgr;-dppm)(2)(CO)(CNXyl)(2)]Y (Y = PF(6), O(3)SCF(3))

The reactions of the unsymmetrical, coordinatively unsaturated dirhenium(II) complexes [Re(2)Br(3)(&mgr;-dppm)(2)(CO)(CNXyl)]Y (XylNC = 2,6-dimethylphenyl isocyanide; Y = O(3)SCF(3) (3a), PF(6) (3b)) with XylNC afford at least three isomeric forms of the complex cation [Re(2)Br(3)(&mgr;-dppm)(2)(CO)(CNXyl)(2)](+). Two forms have very similar bis(&mgr;-halo)-bridged edge-sharing bioctahedral structures of the type [(CO)BrRe(&mgr;-Br)(2)(&mgr;-dppm)(2)Re(CNXyl)(2)]Y (Y = O(3)SCF(3) (4a/4a'), PF(6) (4b/4b')), while the third is an open bioctahedron [(XylNC)(2)BrRe(&mgr;-dppm)(2)ReBr(2)(CO)]Y (Y = O(3)SCF(3) (5a), PF(6) (5b)). While the analogous chloro complex cation [Re(2)Cl(3)(&mgr;-dppm)(2)(CO)(CNXyl)(2)](+) was previously shown to exist in three isomeric forms, only one of these has been found to be structurally similar to the bromo complexes (i.e. the isomer analogous to 5a and 5b). The reaction of 3a with CO gives the salt [Re(2)Br(3)(&mgr;-dppm)(2)(CO)(2)(CNXyl)]O(3)SCF(3) (7), in which the edge-sharing bioctahedral cation [(XylNC)BrRe(&mgr;-Br)(&mgr;-CO)(&mgr;-dppm)(2)ReBr(CO)](+) has an all-cis arrangement of pi-acceptor ligands. The Re-Re distances in the structures of 4b', 5a, and 7 are 3.0456(8), 2.3792(7), and 2.5853(13) ?, respectively, and accord with formal Re-Re bond orders of 1, 3, and 2, respectively. Crystal data for [Re(2)Br(3)(&mgr;-dppm)(2)(CO)(CNXyl)(2)](PF(6))(0.78)(ReO(4))(0.22).CH(2)Cl(2) (4b') at 295 K: monoclinic space group P2(1)/n (No. 14) with a = 19.845(4) ?, b = 16.945(5) ?, c = 21.759(3) ?, beta = 105.856(13) degrees, V = 7038(5) ?(3), and Z = 4. The structure was refined to R = 0.060 (R(w) = 0.145) for 14 245 data (F(o)(2) > 2sigma(F(o)(2))). Crystal data for [Re(2)Br(3)(&mgr;-dppm)(2)(CO)(CNXyl)(2)]O(3)SCF(3).C(6)H(6) (5a) at 173 K: monoclinic space group P2(1)/n (No. 14) with a = 14.785(3) ?, b = 15.289(4) ?, c = 32.067(5) ?, beta = 100.87(2) degrees, V=7118(5) ?(3), and Z = 4. The structure was refined to R = 0.046 (R(w) = 0.055) for 6962 data (I > 3.0sigma(I)). Crystal data for [Re(2)Br(3)(&mgr;-dppm)(2)(CO)(2)(CNXyl)]O(3)SCF(3).Me(2)CHC(O)Me (7) at 295 K: monoclinic space group P2(1)/n (No. 14) with a = 14.951(2) ?, b = 12.4180(19) ?, c = 40.600(5) ?, beta = 89.993(11) degrees, V = 7537(3) ?(3), and Z = 4. The structure was refined to R = 0.074 (R(w) = 0.088) for 6595 data (I > 3.0sigma(I)).     

Synthesis and Characterization of nido-[1,1,2,2-(CO)(4)-1,2-(PPh(3))(2)-1,2-FeIrB(2)H(5)]: A Heterobimetallaborane Analogue of nido-[B(4)H(7)](-)

The synthesis and characterization of nido-[1,1,2,2-(CO)(4)-1,2-(PPh(3))(2)-1,2-FeIrB(2)H(5)] (1) is reported. 1 is formed in low yield as a degradation product from the reaction between [{&mgr;-Fe(CO)(4)}B(6)H(9)](-) and trans-Ir(CO)Cl(PPh(3))(2) in THF and is characterized from NMR, IR, and analytical data and by a single-crystal X-ray diffraction study. 1 crystallizes in the monoclinic space group P2(1)/n with a = 12.8622(12), b = 14.3313(12), c = 23.579(3) ?, beta = 97.12(2) degrees, Z = 4, V = 4257.0(8) ?(3), R(1) = 4.83%, and wR(2)()(F(2)) = 12.43%. The heterobimetallaborane structure may be viewed as a derivative of the binary boron hydride nido-[B(4)H(7)](-) and is related to the known homobimetallatetraborane analogues [Fe(2)(CO)(6)B(2)H(6)] and [Co(2)(CO)(6)B(2)H(4)]. 1 exhibits proton fluxionality in its (1)H NMR spectrum, which is related to that found in the latter two compounds.     

Reaction of bis(phosphine)(hydrotris(3,5-dimethylpyrazolyl)borato)rhodium(I) with phenylacetylene,p-nitrobenzaldehyde,and triphenyltin hydride: structures of [Rh(Tp)(PPh(3))(2)], [Rh(Tp)(H)(C(2)Ph)(P(4-C(6)H(4)F)(3))], [Rh(Tp)(H)(COC(6)H(4)-4-NO(2))(PPh(3))], and [Rh(Tp)(H)(SnPh(3))(PPh(3))

The complexes [Rh(Tp)(PPh(3))(2)] (1a) and [Rh(Tp)(P(4-C(6)H(4)F)(3))(2)] (1b) combine with PhC(2)H, 4-NO(2)-C(6)H(4)CHO and Ph(3)SnH to give [Rh(Tp)(H)(C(2)Ph)(PR(3))] (R = Ph, 2a; R = 4-C(6)H(4)F, 2b), [Rh(Tp)(H)(COC(6)H(4)-4-NO(2))(PR(3))] (R = Ph, 3a), and [Rh(Tp)(H)(SnPh(3))(PR(3))] (R = Ph, 4a; R = 4-C(6)H(4)F, 4b) in moderate to good yield. Complexes 1a, 2b, 3a, and 4a have been structurally characterized. In 1a the Tp ligand is bidentate, in 2b, 3a, and 4a it is tridentate. Crystal data for 1a: space group P2(1)/c; a = 11.9664(19), b = 21.355(3), c = 20.685(3) A; beta = 112.576(7) degrees; V = 4880.8(12) A(3); Z = 4; R = 0.0441. Data for 2b: space group P(-)1; a = 10.130(3), b = 12.869(4), c = 17.038(5) A; alpha = 78.641(6), beta = 76.040(5), gamma = 81.210(6) degrees; V = 2100.3(11) A(3); Z = 2; R = 0.0493. Data for 3a: space group P(-)1; a = 10.0073(11), b = 10.5116(12), c = 19.874(2) A; alpha = 83.728(2), beta = 88.759(2), gamma = 65.756(2) degrees; V =1894.2(4) A(3); Z = 2; R = 0.0253. Data for 4a: space group P2(1)/c; a = 15.545(2), b = 18.110(2), c = 17.810(2) A; beta = 95.094(3) degrees; V = 4994.1(10) A(3); Z = 4; R = 0.0256. NMR data ((1)H, (31)P, (103)Rh, (119)Sn) are also reported.