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

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

Highly Efficient Separation of a Solid Mixture of Naphthalene and Anthracene by a Reusable Porous Metal–Organic Framework through a Single-Crystal-to-Single-Crystal Transformation

The three-dimensional crystalline porous metal–organic framework [Ni2(μ2-OH2)(1,3-BDC)2(tpcb)]n (1) [1,3-H2BDC = 1,3-benzenedicarboxylic acid; tpcb = tetrakis(4-pyridyl)cyclobutane] was used to separate a solid mixture of naphthalene and anthracene at room temperature via selective adsorption of naphthalene. The process involved a single-crystal-to-single-crystal transformation. The guest naphthalene molecules could be exchanged with ethanol, and the host, 1, could be regenerated by removal of the guest ethanol molecules

Highly Efficient Separation of a Solid Mixture of Naphthalene and Anthracene by a Reusable Porous Metal–Organic Framework through a Single-Crystal-to-Single-Crystal Transformation

The three-dimensional crystalline porous metal–organic framework [Ni2(μ2-OH2)(1,3-BDC)2(tpcb)]n (1) [1,3-H2BDC = 1,3-benzenedicarboxylic acid; tpcb = tetrakis(4-pyridyl)cyclobutane] was used to separate a solid mixture of naphthalene and anthracene at room temperature via selective adsorption of naphthalene. The process involved a single-crystal-to-single-crystal transformation. The guest naphthalene molecules could be exchanged with ethanol, and the host, 1, could be regenerated by removal of the guest ethanol molecules

Crystallographic and DFT studies on host-guest complexes consisting of zinc bisporphyrinates and 1-phenylethylamine

We have investigated the chirality transfer from 1-phenylethylamine to a 5-amino-1,3-phthalic acid diamide-linked zinc bisporphyrinate through crystallographic and DFT studies. When the hosts were mixed with optically pure 1-phenylethylamine, CD showed moderate signals in the Soret band region. Single crystals of the corresponding 1:1 and 1:2 host-guest complexes were obtained. We present the first crystallographic structure of a 1:2 host-guest complex consisting of a bisporphyrin host and chiral monoamine guests. The structure reveals that the host-guest interactions are different for two guest molecules. The first guest is involved in a hydrogen bond and π-π interactions, while the second one is only involved in π-π interactions, which has not been observed in previous studies. The corresponding chirality transfer mechanism was also rationalized by DFT calculations. </p

A New Entry into Molybdenum/Tungsten Sulfur Chemistry: Synthesis and Reactions of Mononuclear Sulfido Complexes of Pentamethylcyclopentadienyl−Molybdenum(VI) and −Tungsten(VI)

A series of mononuclear thio complexes of pentamethylcyclopentadienyl−molybdenum(VI) and −tungsten(VI) have been synthesized via C−S bond-cleaving reactions of thiolates. Use of Li2S2 for sulfurization of Cp*MoCl4 resulted in the known dinuclear complex, anti-Cp*2Mo2(S)2(μ-S)2 (1), while the analogous reaction of Cp*WCl4 gave rise to anti-Cp*2W2(S)2(μ-S)2 (2) and (PPh4)[Cp*W(S)3] (3), the latter of which was isolated after the subsequent cation exchange reaction with PPh4Br. In contrast, the reaction of Cp*WCl4 with Li2edt (edt = SCH2CH2S) followed by treatment with PPh4Br generated 3 as the sole isolable product in high yield. A similar reaction between Cp*WCl4 and LiStBu afforded Cp*W(S)2(StBu) (6), which turned out to be thermally unstable in solution and gradually degraded to 2. In these reactions of Cp*WCl4 with lithium thiolates, a facile C−S bond cleavage took place and the tungsten atom was oxidized from W(V) to W(VI). On the other hand, the Mo(IV) thiolate complexes, Cp*Mo(StBu)3 (4) and (PPh4)[Cp*Mo(edt)2] (5), were formed from the Cp*MoCl4/LiStBu and Cp*MoCl4/Li2edt/PPh4Br reaction systems. The complex 4 was readily oxidized by dry O2 producing Cp*Mo(O)2(StBu) (7) exclusively, while the reactions of 4 with NH2NMe2 and NH2NHPh occurred slowly to yield Cp*Mo(S)2(StBu) (8). The hydrazines acted as oxidants, presumably by cleaving the N−N bond, and promoted the C−S bond rupture of tert-butyl thiolate and concomitant oxidation of molybdenum from Mo(IV) to Mo(VI). Elemental sulfur S8 and grey selenium also acted as oxidants in the reactions with 4, leading to a complex mixture of products. From the 4 + S8 reaction, the complexes 1, 8, and Cp*Mo(O)(S)(StBu) (9) were produced, and the 4 + Se reaction lead to 8 and anti-Cp*2Mo2(E)2(μ-E)2 (10; E = S, Se). Finally treatment of 8 with Li2S2 and PPh4Br afforded (PPh4)[Cp*Mo(S)3] (11). We found that 11 was synthesized more easily by a one-pot reaction of 4, 1/4 equiv of S8, and Li2S2 in THF. The trithio complexes, 3 and 11, reacted very cleanly with PhC⋮CPh generating (PPh4)[Cp*M(S)(S2C2Ph2)] (M = W (12), Mo (13)), respectively. A kinetic study of these reactions showed that they were first order in PhC⋮CPh and first order in 3 or 11 with appreciable negative entropies of activation and that the activation barrier was higher for the molybdenum reaction. The crystal structures of 3−8 and 11−13 were determined by the X-ray analysis

A New Entry into Molybdenum/Tungsten Sulfur Chemistry: Synthesis and Reactions of Mononuclear Sulfido Complexes of Pentamethylcyclopentadienyl−Molybdenum(VI) and −Tungsten(VI)

A series of mononuclear thio complexes of pentamethylcyclopentadienyl−molybdenum(VI) and −tungsten(VI) have been synthesized via C−S bond-cleaving reactions of thiolates. Use of Li2S2 for sulfurization of Cp*MoCl4 resulted in the known dinuclear complex, anti-Cp*2Mo2(S)2(μ-S)2 (1), while the analogous reaction of Cp*WCl4 gave rise to anti-Cp*2W2(S)2(μ-S)2 (2) and (PPh4)[Cp*W(S)3] (3), the latter of which was isolated after the subsequent cation exchange reaction with PPh4Br. In contrast, the reaction of Cp*WCl4 with Li2edt (edt = SCH2CH2S) followed by treatment with PPh4Br generated 3 as the sole isolable product in high yield. A similar reaction between Cp*WCl4 and LiStBu afforded Cp*W(S)2(StBu) (6), which turned out to be thermally unstable in solution and gradually degraded to 2. In these reactions of Cp*WCl4 with lithium thiolates, a facile C−S bond cleavage took place and the tungsten atom was oxidized from W(V) to W(VI). On the other hand, the Mo(IV) thiolate complexes, Cp*Mo(StBu)3 (4) and (PPh4)[Cp*Mo(edt)2] (5), were formed from the Cp*MoCl4/LiStBu and Cp*MoCl4/Li2edt/PPh4Br reaction systems. The complex 4 was readily oxidized by dry O2 producing Cp*Mo(O)2(StBu) (7) exclusively, while the reactions of 4 with NH2NMe2 and NH2NHPh occurred slowly to yield Cp*Mo(S)2(StBu) (8). The hydrazines acted as oxidants, presumably by cleaving the N−N bond, and promoted the C−S bond rupture of tert-butyl thiolate and concomitant oxidation of molybdenum from Mo(IV) to Mo(VI). Elemental sulfur S8 and grey selenium also acted as oxidants in the reactions with 4, leading to a complex mixture of products. From the 4 + S8 reaction, the complexes 1, 8, and Cp*Mo(O)(S)(StBu) (9) were produced, and the 4 + Se reaction lead to 8 and anti-Cp*2Mo2(E)2(μ-E)2 (10; E = S, Se). Finally treatment of 8 with Li2S2 and PPh4Br afforded (PPh4)[Cp*Mo(S)3] (11). We found that 11 was synthesized more easily by a one-pot reaction of 4, 1/4 equiv of S8, and Li2S2 in THF. The trithio complexes, 3 and 11, reacted very cleanly with PhC⋮CPh generating (PPh4)[Cp*M(S)(S2C2Ph2)] (M = W (12), Mo (13)), respectively. A kinetic study of these reactions showed that they were first order in PhC⋮CPh and first order in 3 or 11 with appreciable negative entropies of activation and that the activation barrier was higher for the molybdenum reaction. The crystal structures of 3−8 and 11−13 were determined by the X-ray analysis