Molecular understanding of the formation of surface zirconium hydrides upon thermal treatment under hydrogen of [([triple bond]SiO)Zr(CH2tBu)3] by using advanced solid-state NMR techniques

The reaction of [([triple bond]SiO)Zr(CH(2)tBu)(3)] with H(2) at 150 degrees C leads to the hydrogenolysis of the zirconium-carbon bonds to form a very reactive hydride intermediate(s), which further reacts with the surrounding siloxane ligands present at the surface of this support to form mainly two different zirconium hydrides: [([triple bond]SiO)(3)Zr-H] (1a, 70-80%) and [([triple bond]SiO)(2)ZrH(2)] (1b, 20-30%) along with silicon hydrides, [([triple bond]SiO)(3)SiH] and [([triple bond]SiO)(2)SiH(2)]. Their structural identities were identified by (1)H DQ solid-state NMR spectroscopy as well as reactivity studies. These two species react with CO(2) and N(2)O to give, respectively, the corresponding formate [([triple bond]SiO)(4-x)Zr(O-C(=O)H)(x)] (2) and hydroxide complexes [([triple bond]SiO)(4-x)Zr(OH)(x)] (x = 1 or 2 for 3a and 3b, respectively) as major surface complexes.     

Non-oxidative coupling reaction of methane to ethane and hydrogen catalyzed by the silica-supported tantalum hydride: ([triple bond]SiO)2Ta-H

Silica-supported tantalum hydride, (SiO)2Ta-H (1), proves to be the first single-site catalyst for the direct non-oxidative coupling transformation of methane into ethane and hydrogen at moderate temperatures, with a high selectivity (>98%). The reaction likely involves the tantalum-methyl-methylidene species as a key intermediate, where the methyl ligand can migrate onto the tantalum-methylidene affording the tantalum-ethyl.     

Wire-like PtC[triple bond]CC[triple bond]CC[triple bond]CC[triple bond]CPt moieties surrounded by double-helical "insulation": new motifs featuring P(CH2)20P and P(CH2)4O(CH2)2O(CH2)4P linkages

Ring-closing alkene metatheses of trans,trans-(C6F5)(Ph2P-Z-CH=CH2)2Pt(C[triple bond]C)4Pt(Ph2P-Z-CH=CH2)2(C6F5) (Z = (CH2)9, (CH2)4O(CH2)2), followed by hydrogenation, give the title compounds; the former exhibits an exceptionally twisted conformation, and the latter establishes that functional groups can be incorporated into the flexible sp3 chain.     

Aliphatic and aromatic carbon-fluorine bond activation with Cp*(2)ZrH(2): mechanisms of hydrodefluorination.

Cp*(2)ZrH(2) (1) (Cp* = pentamethylcyclopentadienyl) reacts with primary, secondary, and tertiary monofluorinated aliphatic hydrocarbons to give Cp*(2)ZrHF (2) and/or Cp*(2)ZrF(2) and alkane quantitatively through a radical chain mechanism. The reactivity of monofluorinated aliphatic C-F bonds decreases in the order 1 degrees > 2 degrees > 3 degrees. The rate of hydrodefluorination was also greatly reduced with -CF(2)H and -CF(3) groups attached to the hydrocarbon. An atmosphere of H(2) is required to stabilize 1 against C-H activation of the Cp*-methyl groups and subsequent dimerization under the thermal conditions employed in these reactions. Reaction of 1 with fluorobenzene cleanly forms a mixture of Cp*(2)ZrHF, benzene, and Cp*(2)Zr(C(6)H(5))F. Detailed studies indicate that radicals are not involved in this aromatic C-F activation reaction and that dual hydrodefluorination pathways are operative. In one mechanism, hydridic attack by Cp*(2)ZrH(2) on the aromatic ring and fluoride abstraction is involved. In the second mechanism, an initial ortho C-H activation occurs, followed by beta-fluoride elimination to generate a benzyne complex, which then inserts into the zirconium-hydride bond.     

Osmabenzenes from the reactions of HC[triple bond]CCH(OH)C[triple bond]CH with OsX2(PPh3)3 (X = Cl, Br)

Treatment of OsX2(PPh3)3 (X = Cl, Br) with HCCCH(OH)CCH in THF produces OsX2(CH=C(PPh3)CH(OH)CCH)(PPh3)2, which reacts with PPh3 to give osmabenzenes [Os(CHC(PPh3)CHC(PPh3)CH)X2(PPh3)2]+.     

Synthesis and luminescence behaviour of novel heterodecanuclear silver(I)-rhenium(I) alkynyl complexes. X-ray crystal structures of [Ag6(mu-dppm)4[mu3-C[triple bond]CC[triple bond]C-Re(Me2bpy)(CO)3]4](PF6)2 and [Ag6(mu-dppm)4[mu3-C[triple bond]CC[triple bond]C-Re(Br2phen)(CO)3]4](PF6)2

A novel series of luminescent heterodecanuclear mixed-metal alkynyl complexes, [Ag6(mu-dppm)4[mu3-C[triple bond]CC[triple bond]C-Re(N--N)(CO)3]4](PF6)2, (N--N = tBu2bpy, Me2bpy, phen, Br2phen), have been successfully synthesized; the X-ray crystal structures of [Ag6(mu-dppm)4[mu3-C[triple bond]CC[triple bond]C-Re(Me2bpy)(CO)3]4](PF6)2 and [Ag6(mu-dppm)4[mu3-C[triple bond]CC[triple bond]C-Re(Br2phen)(CO)3]4](PF6)2 have also been determined.     

Isopropylammonium Layered Uranyl Chromates: Syntheses and Crystal Structures of [(CH3)2CHNH3]3[(UO2)3(CrO4)2O(OH)3] and[(CH3)2CHNH3]2[(UO2)2(CrO4)3(H2O)]

Two novel isopropylamine‐templated uranyl chromates, [(CH₃)₂CHNH₃]₃[(UO₂)₃(CrO₄)₂O(OH)₃] ( 1 ) and [(CH₃)₂CHNH₃]₂[(UO₂)₂(CrO₄)₃(H₂O)] ( 2 ) were prepared by hydrothermal method at 100 °C. The compounds were characterized by electron microprobe analysis and X‐ray diffraction crystal structure analysis [ 1 : trigonal, P31m, a = 9.646(4), c = 8.469(4) Å, V = 682.4(5) ų; 2 : monoclinic, P2₁/c, a = 11.309(3), b = 11.465(3), c = 17.055(5) Å, β = 99.150(6)°, V = 2183.2(11) ų]. The structure of 1 is based upon trimers of uranyl bipyramids interlinked by CrO₄ tetrahedra to form [(UO₂)₃(CrO₄)₂O(OH)₃]^3– layers, whereas, in the structure of 2 , UO₇ and UO₆(H₂O) pentagonal bipyramids are linked through CrO₄ tetrahedra into the [(UO₂)₂(CrO₄)₃(H₂O)]^2– layers. The structures show many similarities to related uranyl selenate compounds, thus providing additional data on similarities and differences between uranyl sulfates, chromates, selenates, and molybdates.     

Carbon-rich molecules: synthesis and isolation of aryl/heteroaryl terminal bis(butadiynes) (HC[triple bond]C-C[triple bond]C-Ar-C[triple bond]C-C[triple bond]CH) and their applications in the synthesis of oligo(arylenebutadiynylene) molecular wires

The synthesis, isolation and characterisation are reported for a series of terminal aryl/heteroaryl bis(butadiynes) (HC[triple bond]C-C[triple bond]C-Ar-C[triple bond]C-C[triple bond]CH) 4a-e including the X-ray molecular structure of the 2,5-pyridylene derivative 4d; compound 4a and the mono-protected analogue [HC[triple bond]C-C[triple bond]C-Ar-C[triple bond]C-C[triple bond]C-C(OH)Me2] 5a serve as convenient precursors for the synthesis of highly-conjugated oligo(arylenebutadiynylene)s.     

Synthesis of ((t)Bu3SiNH)2ClW triple bond WCl(NHSi(t)Bu3)2 and its degradation via NH bond activation.

Treatment of NaW2Cl7(THF)5 with 4 equiv of (t)Bu3SiNHLi afforded the C2 W(III) dimer [((t)Bu3SiNH)2WCl]2 (1, d(W triple bond W) = 2.337(2) A), which is a rare, primary amide M2X4Y2 species. Its degradation provided evidence of NH bond activation by the ditungsten bond. Addition of 2 equiv of (t)Bu3SiNHLi or TlOSi(t)Bu3 to 1 yielded H2 and hydride ((t)Bu3SiN)2((t)Bu3SiNH)WH (2, d(WH) = 1.67(3) A) or ((t)Bu3SiN)2((t)Bu3SiO)WH (3). Thermolysis (60 degrees C, 16 h) of 1 in py gave ((t)Bu3SiN)2WHCl(py) (4-py, 40-50%), ((t)Bu3SiN)2WCl2(py) (6-py, 10%), and ((t)Bu3SiN)2HW(mu-Cl)(mu-H)2W(NSi(t)Bu3)py2 (5-py2, 5%), whereas thermolysis in DME produced ((t)Bu3SiN)2WCl(OMe) (7, 30%), ((t)Bu3SiN)2WCl2 (6, 20%), and ((t)Bu3SiN)2HW(mu-Cl)(mu-H)2W(NSi(t)Bu3)DME (5-DME, 3%). Compound 7 was independently produced via thermolysis of 4-py and DME (-MeOEt, -py), and THF and ethylene oxide addition to hydride 2 gave ((t)Bu3SiN)2((t)Bu3SiNH)WO(n)Bu (8) and ((t)Bu3SiN)2((t)Bu3SiNH)WOEt (9), respectively. Dichloride 6 was isolated from SnCl4 treatment of 1 with the loss of H2. Sequential NH bond activations by the W2 core lead to "((t)Bu3SiN)2WHCl" (4) and subsequent thermal degradation products. Thermolysis of 1 in the presence of H2C=CH(t)Bu and PhC triple bond CPh trapped 4 and generated ((t)Bu3SiN)2W((neo)Hex)Cl (10) and a approximately 6:1 mixture of ((t)Bu3SiN)2WCl(cis-CPh=CPhH) (11-cis) and ((t)Bu(3)SiN)2WCl(trans-CPh=CPhH) (11-trans), respectively. Thermolysis of the latter mixture afforded ((t)Bu3SiNH)((t)Bu3SiN)WCl(eta2-PhCCPh) (12) as the major constituent. Alkylation of 1 with MeMgBr produced ((t)Bu3SiN)2W(CH3)2 (13), as did addition of 2 equiv of MeMgBr to 6. X-ray crystal structure determinations of 1, 2, 5-py2, 6-py, 11-trans, and 12 confirmed spectroscopic identifications. A general mechanism that features a sequence of NH activations to generate 4, followed by chloride metathesis, olefin insertion, etc., explains the formation of all products.     

The C-H activation of methane by laser-ablated zirconium atoms: CH2=ZrH2, the simplest carbene hydride complex, agostic bonding, and (CH3)2ZrH2

Reaction of laser-ablated Zr with CH(4) ((13)CH(4), CD(4), and CH(2)D(2)) in excess neon during condensation at 5 K forms CH(2)=ZrH(2), the simplest alkylidene hydride complex, which is identified by infrared absorptions at 1581.0, 1546.2, 757.0, and 634.5 cm(-)(1). Density functional theory electronic structure calculations using a large basis set with polarization functions predict a C(1) symmetry structure with agostic C-H- - -Zr bonding and distance of 2.300 A. Identification of the agostic CH(2)=ZrH(2) methylidene complex is confirmed by an excellent match of calculated and observed isotopic frequencies particularly for the four unique CHD=ZrHD isotopic modifications. The analogous reactions in excess argon give two persistent photoreversible matrix configurations for CH(2)=ZrH(2). Finally, methane activation by CH(2)=ZrH(2) gives the new (CH(3))(2)ZrH(2) molecule.     

Synthesis, photophysics, electrochemistry, theoretical, and transient absorption studies of luminescent copper(I) and silver(I) diynyl complexes. X-ray crystal structures of [Cu3(micro-dppm)3(micro3-eta1-C triple bond CC triple bond CPh)2]PF6 and [Cu3(micro-dppm)3(micro3-eta1-C triple bond CC triple bond CH)2]PF6

A series of soluble trinuclear copper(I) and silver(I) complexes containing bicapped diynyl ligands, [M(3)(micro-dppm)(3)(micro(3)-eta(1)-C triple bond CC triple bond CR)(2)]PF(6) (M = Cu, R = Ph, C(6)H(4)-CH(3)-p, C(6)H(4)-OCH(3)-p, (n)C(6)H(13), H; M = Ag, R = Ph, C(6)H(4)-OCH(3)-p), has been synthesized and their electronic, photophysical, and electrochemical properties studied. The X-ray crystal structures of [Cu(3)(micro-dppm)(3)(micro(3)-eta(1)-C triple bond CC triple bond CPh)(2)]PF(6) and [Cu(3)(micro-dppm)(3)(micro(3)-eta(1)-C triple bond CC triple bond CH)(2)]PF(6) have been determined.     

Pr5F[SiO4]2[SeO3]3: Another Complex Fluoride Oxosilicate Oxoselenate(IV)

During attempts to synthesize lanthanoid(III) fluoride oxoselenates(IV) with the simple composition MF[SeO₃], not only Pr₃F[SeO₃]₄, but also Pr₅F[SiO₄]₂[SeO₃]₃ appeared as pale green crystalline by‐products in the case of praseodymium. Pr₅F[SiO₄]₂[SeO₃]₃ crystallizes triclinically in space group P$\bar{1}$ (no. 2) with a = 701.14(5), b = 982.68(7), c = 1286.79(9) pm, α = 70.552(3), β = 76.904(3), γ = 69.417(3)° and Z = 2. The five crystallographically different Pr³⁺ cations on the general positions 2i show coordination numbers of eight and nine. [(Pr1)O₈]^13– and [(Pr2)O₈]^13– polyhedra are connected to$\bar{1}$ {[(Pr1, 2)₂O₁₂]^18–} chains along the [100] direction. [(Pr3)O₇F]^12–, [(Pr4)O₈F]^14– and [(Pr4)O₈F]^14– polyhedra generate [F(Pr3, 4, 5)₃O₁₉]^30– units about their central F^– anion in triangular Pr³⁺ coordination. These units form $\bar{1}$ {[F(Pr3, 4, 5)₃O₁₆]^24–} strands, again running parallel to [100]. Their alternating connection with the $\bar{1}$ {[(Pr1, 2)₂O₁₂]^18–} chains results in $\bar{1}$ {[Pr₅O₂₀F]^26–} sheets parallel to the (001) plane. Like in the already known related compound Er₃F[SiO₄][SeO₃]₂, a three‐dimensional network $\bar{1}$ {[Pr₅O₁₇F]^20–} is achieved without the contribution of both the tetravalent silicon and selenium components. However, two Si⁴⁺ and three Se⁴⁺ cations forming tetrahedral [SiO₄]^4– and ψ¹‐tetrahedral [SeO₃]^2– units with all O^2– anions guarantee the charge balance. The formation of Pr₅F[SiO₄]₂[SeO₃]₃ was observed when praseodymium sesquioxide (Pr₂O₃: in‐situ produced from Pr and Pr₆O₁₁ in a molar ratio of ³/₁₁:⁴/₁₁),praseodymium trifluoride (PrF₃) and selenium dioxide (SeO₂) in 1:1:3 molar ratios were reacted with CsBr as fluxing agent for five days at 750 °C in evacuated fused silica (SiO₂) ampoules.     

Syntheses and structures of metallocene methyltrihydroborate derivativies: Cp2ZrCl[(mu-H)2BHCH3], Cp2Zr[(mu-H)2BHCH3]2, and Cp2Ti[(mu-H)2BHCH3

In reactions of zirconocene dichloride, Cp(2)ZrCl(2), with 1 equiv and an excess amount of LiBH(3)CH(3), the methyltrihydroborate complexes, Cp(2)ZrCl[(mu-H)(2)BHCH(3)], 1, and Cp(2)Zr[(mu-H)(2)BHCH(3)](2), 2, were isolated. The reaction of titanocene dichloride, Cp(2)TiCl(2), with an excess amount of LiBH(3)CH(3) produced the monosubstituted methyltrihydroborate complex, Cp(2)Ti[(mu-H)(2)BHCH(3)], 3. The titanium was reduced from Ti(IV) to Ti(III), producing a 17-electron, paramagnetic titanocene complex. Under a dynamic vacuum at room temperature, compound 2 decomposed and produced the zirconium hydride compound Cp(2)ZrH[(mu-H)(2)BHCH(3)]. Single crystal X-ray structures of 1, 2, and 3 were determined. Crystal data for 1: space group P2(1)/c, a = 13.7921(3) A, b = 13.4227(3) A, c = 13.0868(3) A, beta = 91.6448(12) degrees, Z = 8. Crystal data for 2: space group Pna2(1), a = 15.2949(4) A, b = 9.3417(2) A, c = 9.3211(2) A, Z = 4. Crystal data for 3: space group Fmm2, a = 9.1795(3) A, b = 13.0993(5) A, c = 8.8520(3) A, Z = 4.     

Characterization of low molecular weight components of [(ViMe2SiO1/2)x(PhSiO3/2)y(SiO4/2)z], [(ViMe2SiO1/2)x(SiO4/2)y], and [(SiO4/2)x(HO1/2)y(tBuO1/2)z] silsesquioxanes by electrospray ionization fourier transform mass spectrometry (ESI-FTMS)

This paper describes the characterization of low molecular weight components of four materials using electrospray ionization Fourier transform mass spectrometry (ESI-FTMS). The materials in the current study are [(ViMe₂SiO_1/2)_x(PhSiO_3/2)_y(SiO_4/2)_z] (MTQ), [(ViMe₂SiO_1/2)_x(SiO_4/2)_y] (MQ), and [(SiO_4/2)_x(HO_1/2)_y(^tBuO_1/2)_z] (Q) silsesquioxanes. Accurate mass measurements coupled with knowledge of resin chemistry afforded siloxane composition determination that was used to propose specific structures for the oligomers. Branched or linear (T_nQ_mM_n+2m+2), and monocyclic (T_nQ_mM_n+2m) structures are predominant structures for the low molecular weight species in MTQ. For MQ and Q, more condensed structures, such as partially opened cage structures (Q_mM_2m?6 and Q_mM_2m?8), were identified. The differences between MQ, Q, and MTQ are likely attributed to differences in intrinsic structure and reactivity of T and Q building blocks. The structural information obtained for these oligomeric species will ultimately provide a better understanding of new resin materials and their associated physical properties.     

The butterfly dimer [(tBu3SiO)Cr]2(mu-OSitBu3)2 and its oxidative cleavage to (tBu3SiO)2Cr(=N-N=CPh2)2 and (tBu3SiO)2Cr=N(2,6-Ph2-C6H3)

Treatment of CrCl2(THF)2 with NaOSitBu3 afforded the butterfly dimer [(tBu3SiO)Cr]2(mu-OSitBu3)2 (1(2)), whose d(CrCr) of 2.658(31) A and magnetism were indicative of strong antiferromagnetic coupling. A Boltzmann distribution of low-energy 1A1, 3B1, 5A1, 7B1, and 9A1 states obtained from calculations on [(HO)2Cr]2(muOH)2 (1'(2)) were used to provide a reasonable fit of the mu(eff) vs T data. Cleavage of 1(2) with various L (L = 4-picoline, p-tolunitrile, tBuCN, tBuNC, Ph2CO, and PMe3) generated (tBu3SiO)2CrL2 (1-L2). The dimer was oxidatively severed by Ph2CN2 to give (tBu3SiO)2Cr(N2CPh2)2 (2) and by RN3 at 23 degrees C to afford (silox)2Cr=NR (3-R) for bulky R (adamantyl (Ad), 2,6-iPr2-C6H3, 2,4,6-Me3-C6H2 = Mes, 2,6-Ph2-C6H3) and (tBu3SiO)2Cr(=NR)2 (4-R) for smaller substituents (R = 1-Naph, 2-Anth). X-ray structural studies were conducted on 1(2), square planar 1-(OCPh2)2, pseudo-Td 2 and pseudo-trigonal 3-(2,6-Ph2-C6H3), whose S = 1 ground state was discussed on the basis of calculations of (H3SiO)2Cr=NPh (3' '-Ph).     

Synthesis and crystal structures of zirconium(IV) nitrate complexes (NO2)[Zr(NO3)3(H2O)3]2(NO3) 3, Cs[Zr(NO3)5], and (NH4)[Zr(NO3)5](HNO3)

The zirconium nitrate complexes (NO₂)[Zr(NO₃)₃(H₂O)₃]₂(NO₃)₃ (1), Cs[Zr(NO₃)₅] ((2), (NH₄)[Zr(NO₃)₅](HNO₃) (3), and (NO₂)_0.23(NO)_0.77[Zr(NO₃)₅] ((4) were prepared by crystallization from nitric acid solutions in the presence of H₂SO₄ or P₂O₅. The complexes were characterized by X-ray diffraction. The crystal structure of 1 consists of nitrate anions, nitronium cations, and [Zr(NO₃)₃(H₂O)₃]⁺ complex cations in which the Zr^IV atom is coordinated by three water molecules and three bidentate nitrate groups. The coordination polyhedron of the Zr^IV atom is a tricapped trigonal prism formed by nine oxygen atoms. The island structures of 2 and 3 contain [Zr(NO₃)₅]^? anions and Cs⁺ or NH₄ ⁺ cations, respectively. In addition, complex 3 contains HNO₃ molecules. Complex 4 differs from (NO₂)[Zr(NO₃)₅] in that three-fourth of the nitronium cations in 4 are replaced by nitrosonium cations NO⁺, resulting in a decrease in the unit cell parameters. In the [Zr(NO₃)₅]^? anion involved in complexes 2–4, the Zr^IV atom is coordinated by five bidentate nitrate groups and has an unusually high coordination number of 10. The coordination polyhedron is a bicapped square antiprism.