Phoenix

A novel chiral coordination polymer, [Cu­(C₆H₅CH­(OH)­COO)­(μ-C₆H₅CH­(OH)­COO)] (<b>1</b>-L and <b>1</b>-D), was synthesized through a reaction of copper acetate with l-mandelic acid at room temperature. Although previously reported copper mandelate prepared by hydrothermal reaction was a centrosymmetric coordination polymer because of the racemization of mandelic acid, the current coordination polymer shows noncentrosymmetry and a completely different structure from that previously reported. The X-ray crystallography for <b>1</b>-L revealed that the copper center of the compound showed a highly distorted octahedral structure bridged by a chiral mandelate ligand in the unusual coordination mode to construct a one-dimensional (1D) zigzag chain structure. These 1D chains interdigitated each other to give a layered structure as a result of the formation of multiple aromatic interactions and hydrogen bonds between hydroxyl and carboxylate moieties at mandelate ligands. The coordination polymer <b>1</b>-L belongs to the noncentrosymmetric space group of C2 to show piezoelectric properties and second harmonic generation (SHG) activity

Synthesis of (Pentamethylcyclopentadienyl)tantalum Sulfido Complexes via C−S Bond Cleavage of Triphenylmethanethiolate and Formation of a Novel Trithioborato Ligand

Treatment of Cp*TaCl4 with triphenylmethanethiol via C−S bond cleavage gave rise to Cp*TaCl(S)(SCPh3) (1), which was treated with LiSR, Li2S, and NaBH4 to afford Cp*TaS(SR)(SCPh3) (R = CPh3 (2), CMe3 (3)), [Cp*Ta(S)3Li2(THF)2]2 (4), and Cp*3Ta3(S)3(S3BH) (5), respectively. The crystal structures of 1 and 5 were determined by X-ray diffraction

Alkylation Reactions of [WS₄]^2- and [(η⁵-C₅Me₅)WS₃]^- with 2,6-Bis(bromomethyl)pyridine: The First Isolation of Bisalkylated Tetrathiometalate WS₂{2,6-(SCH₂)₂(C₅H₃N)}

The trithio and tetrathio complexes of tungsten (PPh4)[Cp*WS3] (Cp* = η5-C5Me5) and (PPh4)2[WS4] undergo alkylation reactions with 2,6-bis(bromomethyl)pyridine to yield [(Cp*WS2)2{2,6-(SCH2)2(C5H3N)}]·CH3CN (1·CH3CN) (73.1% yield) and WS2{2,6-(SCH2)2(C5H3N)} (2) (76.0% yield), respectively. In the dinuclear complex 1, two Cp*WS3 units are linked by a 2,6-dimethylenepyridine bridge, and the pyridine nitrogen is not coordinated at tungsten. Complex 2 is the first example of bisalkylated tetrathiometalates, the mononuclear structure of which is stabilized by coordination of the pyridine nitrogen

Low Temperature Solid-State Reactions of (NH₄)₂[MS₄] (M = W, Mo) with [Cu(CH₃CN)₄](PF₆) and CuBr in the Presence of Bis(diphenylphosphino)methane (dppm): Crystal Structures of [MS₄Cu₄(dppm)₄](PF₆)₂ (M = W, Mo), [WS₄Cu₃(dppm)₃]X (X = PF₆, Br), [Cu₃(dppm)₃Br₂]Br, [WS₄Cu₂(dppm)₃], and [(n-Bu)₄N][WS₄Cu₃Br₂(dppm)₂]

The solid-state reactions of (NH4)2[MS4] (M = W, Mo), [Cu(CH3CN)4](PF6), and bis(diphenylphosphino)methane (dppm) at 110 °C produced pentanuclear clusters [MS4Cu4(dppm)4](PF6)2 (1, M = W; 2, M = Mo), while the analogous solution reaction in CH2Cl2 for M = W yielded a tetranuclear cluster [WS4Cu3(dppm)3](PF6) (3). On the other hand, the (NH4)2[WS4]/CuBr/dppm reaction system resulted in the formation of a tetranuclear cluster [WS4Cu3(dppm)3]Br (4) either in solid at 110 °C or in CH2Cl2, where the solid-state reaction gave also [Cu3(dppm)3Br2]Br (5) as a side product. When the solid-state reactions between (NH4)2[WS4], [Cu(CH3CN)4](PF6) (or CuBr), and dppm were carried out under the presence of [(n-Bu)4N]Br, [WS4Cu2(dppm)3] (6) and [(n-Bu)4N][WS4Cu3Br2(dppm)2] (7) were generated, respectively, while the corresponding solution reactions in CH2Cl2 gave rise to 3 and 4. Compounds 1−7 were fully characterized. 1 crystallizes in the orthorhombic space group Pnma with a = 37.871(6) Å, b = 19.667(4) Å, c = 14.836(4) Å, and Z = 4. 2 crystallizes in the orthorhombic space group Pnma with a = 38.00(3) Å, b = 19.65(1) Å, c = 14.80(1) Å, and Z = 4. 3·CH2Cl2 crystallizes in the monoclinic space group P21 with a = 13.185(5) Å, b = 17.234(6) Å, c = 17.791(2) Å, β = 90.83(4)°, and Z = 2. 4·CH2Cl2 crystallizes in the monoclinic space group P21 with a = 12.94(2) Å, β = 17.06(1) Å, c = 17.875(7) Å, b = 93.7(1)°, and Z = 2. 5·2(CH3)2CHOH crystallizes in the triclinic space group P1̄ with a = 15.613(5) Å, β = 18.440(6) Å, c = 14.191(8) Å, α = 99.86(4)°, β = 104.14(4)°, γ = 86.79(3)°, and Z = 2. 6·CH2Cl2 crystallizes in the triclinic space group P1̄ with a = 14.60(3) Å, b = 25.6(1) Å, c = 10.98(1) Å, α = 92.9(3)°, β = 105.1(1)°, γ = 78.7(4)°, and Z = 2. 7·1.5CH2Cl2 crystallizes in the monoclinic space group P21/n with a = 10.842(3) Å, b = 31.08(2) Å, c = 22.713(5) Å, β = 101.29(2)°, and Z = 4

Aggregation of the Half-Sandwich Trisulfido Complex of Tungsten with Silver Ions: Synthesis of a Cyanide-Bridged Helical Polymer {[(<i>η</i>⁵-C₅Me₅)WS₃]₂Ag₃(CN)}_∞ and a Cyclic Cluster [(<i>η</i>⁵-C₅Me₅)WS₃Ag]₄

Aggregation of the Half-Sandwich Trisulfido Complex of Tungsten with Silver Ions:  Synthesis of a Cyanide-Bridged Helical Polymer {[(η5-C5Me5)WS3]2Ag3(CN)}∞ and a Cyclic Cluster [(η5-C5Me5)WS3Ag]4</sub

Assembly of Three WS₃Cu₂ Cluster Units by μ₃-S Bridges: Synthesis of [PPh₄][{(C₅Me₅)WS₃Cu₂}₃S₂]

Assembly of Three WS3Cu2 Cluster Units by μ3-S Bridges:  Synthesis of [PPh4][{(C5Me5)WS3Cu2}3S2

Low Temperature Solid-State Reactions of (NH₄)₂[MS₄] (M = W, Mo) with [Cu(CH₃CN)₄](PF₆) and CuBr in the Presence of Bis(diphenylphosphino)methane (dppm): Crystal Structures of [MS₄Cu₄(dppm)₄](PF₆)₂ (M = W, Mo), [WS₄Cu₃(dppm)₃]X (X = PF₆, Br), [Cu₃(dppm)₃Br₂]Br, [WS₄Cu₂(dppm)₃], and [(n-Bu)₄N][WS₄Cu₃Br₂(dppm)₂]

The solid-state reactions of (NH4)2[MS4] (M = W, Mo), [Cu(CH3CN)4](PF6), and bis(diphenylphosphino)methane (dppm) at 110 °C produced pentanuclear clusters [MS4Cu4(dppm)4](PF6)2 (1, M = W; 2, M = Mo), while the analogous solution reaction in CH2Cl2 for M = W yielded a tetranuclear cluster [WS4Cu3(dppm)3](PF6) (3). On the other hand, the (NH4)2[WS4]/CuBr/dppm reaction system resulted in the formation of a tetranuclear cluster [WS4Cu3(dppm)3]Br (4) either in solid at 110 °C or in CH2Cl2, where the solid-state reaction gave also [Cu3(dppm)3Br2]Br (5) as a side product. When the solid-state reactions between (NH4)2[WS4], [Cu(CH3CN)4](PF6) (or CuBr), and dppm were carried out under the presence of [(n-Bu)4N]Br, [WS4Cu2(dppm)3] (6) and [(n-Bu)4N][WS4Cu3Br2(dppm)2] (7) were generated, respectively, while the corresponding solution reactions in CH2Cl2 gave rise to 3 and 4. Compounds 1−7 were fully characterized. 1 crystallizes in the orthorhombic space group Pnma with a = 37.871(6) Å, b = 19.667(4) Å, c = 14.836(4) Å, and Z = 4. 2 crystallizes in the orthorhombic space group Pnma with a = 38.00(3) Å, b = 19.65(1) Å, c = 14.80(1) Å, and Z = 4. 3·CH2Cl2 crystallizes in the monoclinic space group P21 with a = 13.185(5) Å, b = 17.234(6) Å, c = 17.791(2) Å, β = 90.83(4)°, and Z = 2. 4·CH2Cl2 crystallizes in the monoclinic space group P21 with a = 12.94(2) Å, β = 17.06(1) Å, c = 17.875(7) Å, b = 93.7(1)°, and Z = 2. 5·2(CH3)2CHOH crystallizes in the triclinic space group P1̄ with a = 15.613(5) Å, β = 18.440(6) Å, c = 14.191(8) Å, α = 99.86(4)°, β = 104.14(4)°, γ = 86.79(3)°, and Z = 2. 6·CH2Cl2 crystallizes in the triclinic space group P1̄ with a = 14.60(3) Å, b = 25.6(1) Å, c = 10.98(1) Å, α = 92.9(3)°, β = 105.1(1)°, γ = 78.7(4)°, and Z = 2. 7·1.5CH2Cl2 crystallizes in the monoclinic space group P21/n with a = 10.842(3) Å, b = 31.08(2) Å, c = 22.713(5) Å, β = 101.29(2)°, and Z = 4

Low Temperature Solid-State Reactions of (NH₄)₂[MS₄] (M = W, Mo) with [Cu(CH₃CN)₄](PF₆) and CuBr in the Presence of Bis(diphenylphosphino)methane (dppm): Crystal Structures of [MS₄Cu₄(dppm)₄](PF₆)₂ (M = W, Mo), [WS₄Cu₃(dppm)₃]X (X = PF₆, Br), [Cu₃(dppm)₃Br₂]Br, [WS₄Cu₂(dppm)₃], and [(n-Bu)₄N][WS₄Cu₃Br₂(dppm)₂]

The solid-state reactions of (NH4)2[MS4] (M = W, Mo), [Cu(CH3CN)4](PF6), and bis(diphenylphosphino)methane (dppm) at 110 °C produced pentanuclear clusters [MS4Cu4(dppm)4](PF6)2 (1, M = W; 2, M = Mo), while the analogous solution reaction in CH2Cl2 for M = W yielded a tetranuclear cluster [WS4Cu3(dppm)3](PF6) (3). On the other hand, the (NH4)2[WS4]/CuBr/dppm reaction system resulted in the formation of a tetranuclear cluster [WS4Cu3(dppm)3]Br (4) either in solid at 110 °C or in CH2Cl2, where the solid-state reaction gave also [Cu3(dppm)3Br2]Br (5) as a side product. When the solid-state reactions between (NH4)2[WS4], [Cu(CH3CN)4](PF6) (or CuBr), and dppm were carried out under the presence of [(n-Bu)4N]Br, [WS4Cu2(dppm)3] (6) and [(n-Bu)4N][WS4Cu3Br2(dppm)2] (7) were generated, respectively, while the corresponding solution reactions in CH2Cl2 gave rise to 3 and 4. Compounds 1−7 were fully characterized. 1 crystallizes in the orthorhombic space group Pnma with a = 37.871(6) Å, b = 19.667(4) Å, c = 14.836(4) Å, and Z = 4. 2 crystallizes in the orthorhombic space group Pnma with a = 38.00(3) Å, b = 19.65(1) Å, c = 14.80(1) Å, and Z = 4. 3·CH2Cl2 crystallizes in the monoclinic space group P21 with a = 13.185(5) Å, b = 17.234(6) Å, c = 17.791(2) Å, β = 90.83(4)°, and Z = 2. 4·CH2Cl2 crystallizes in the monoclinic space group P21 with a = 12.94(2) Å, β = 17.06(1) Å, c = 17.875(7) Å, b = 93.7(1)°, and Z = 2. 5·2(CH3)2CHOH crystallizes in the triclinic space group P1̄ with a = 15.613(5) Å, β = 18.440(6) Å, c = 14.191(8) Å, α = 99.86(4)°, β = 104.14(4)°, γ = 86.79(3)°, and Z = 2. 6·CH2Cl2 crystallizes in the triclinic space group P1̄ with a = 14.60(3) Å, b = 25.6(1) Å, c = 10.98(1) Å, α = 92.9(3)°, β = 105.1(1)°, γ = 78.7(4)°, and Z = 2. 7·1.5CH2Cl2 crystallizes in the monoclinic space group P21/n with a = 10.842(3) Å, b = 31.08(2) Å, c = 22.713(5) Å, β = 101.29(2)°, and Z = 4

Synthesis of Coordinatively Unsaturated Mesityliron Thiolate Complexes and Their Reactions with Elemental Sulfur

The reactions of Fe2Mes4 (1; Mes = mesityl) with bulky thiols, namely, HSDmp (Dmp = 2,6-dimesitylphenyl), HSDxp (Dxp = 2,6-dixylylphenyl), and HSBtip [Btip = 2,6-(2,4,6-iPr3C6H2)2C6H3], provided a series of iron(II) mesityl complexes bearing bulky thiolate ligands. These iron complexes are the thiolate-bridged dinuclear complexes Fe2Mes2(μ-SAr)(μ-Mes) (2a, Ar = Dmp; 2b, Ar = Dxp), the 1,2-dimethoxyethane (DME) adducts (DME)Fe(SAr)(Mes) (3a, Ar = Dmp; 3b, Ar = Dxp), the mixed-valence FeI−FeII dinuclear complexes (Mes)Fe(μ-SAr)(μ-SAr)Fe (4a, Ar = Dmp; 4b, Ar = Dxp), and a low-coordinate mononuclear complex (BtipS)Fe(Mes) (5). An [Fe8S7] cluster [Fe4S3(SDmp)]2(μ-SDmp)2(μ-SMes)(μ6-S) (6), the core structure of which is topologically relevant to that of the FeMo-cofactor of nitrogenase, was obtained from the reaction of 3a or 4a with S8. The μ-SMes ligand in 6 is formed via insertion of a sulfur atom into the Fe−C(Mes) bond. The formation of cluster 6 from 3a or 4a demonstrates that organoiron complexes are applicable as precursors for iron−sulfur clusters

Reversible Heterolysis of H₂ Mediated by an M−S(Thiolate) Bond (M = Ir, Rh): A Mechanistic Implication for [NiFe] Hydrogenase

Reversible Heterolysis of H2 Mediated by an M−S(Thiolate) Bond (M = Ir, Rh): A Mechanistic Implication for [NiFe] Hydrogenas