Preparation and Reactivity of Mo(NCMe)(η2‐C2Ph2)2(η4‐C4Ph4)

Reaction of Mo(CO)(η²‐C₂Ph₂)₂(η⁴‐C₄Ph₄) and Me₃NO in acetonitrile solvent affords Mo(NCMe)(η²‐C₂Ph₂)₂(η⁴‐C₄Ph₄) 1 . Compound 1 reacts with trimethylphosphine to produce Mo(PMe₃)(η²‐C₂Ph₂)₂(η⁴‐C₄Ph₄) 2 , or reacts with diphenylacetylene to produce (η⁵‐C₅Ph₅)₂Mo 3 and Mo(η²‐O₂CPh)(η⁴‐C₄Ph₄H)(η⁴‐C₄Ph₄) 4 . The molecular structures of 1, 2 and 4 have been determined by an X‐ray diffraction study.     

Azidokomplexe von Vanadium(IV) und Vanadium(V): (Ph4P)2[VOCl2(μ‐N3)]2 und (Ph4P)2[VOCl(μ‐N3)(N3)2]2

Azido Complexes of Vanadium(IV) and Vanadium(V): (Ph₄P)₂[VOCl₂(μ‐N₃)]₂ and (Ph₄P)₂[VOCl(μ‐N₃)(N₃)₂]₂ (Ph₄P)₂[VOCl₂(μ‐N₃)]₂ ( 1 ) was prepared by reaction of (Ph₄P)[VO₂Cl₂] with trimethylsilylazide in the molar ratio 1:2 in dichloromethane solution to give dark green, moisture sensitive, non‐explosive single crystals. The reaction is accompanied by the formation of the dark blue side‐product (Ph₄P)₂[VOCl(μ‐N₃)(N₃)₂]₂ ( 2a ), which can be obtained as the main product by application of a large excess of Me₃SiN₃. Dark blue needles of 2a crystallize spontaneously from the CH₂Cl₂ solution within one hour at 4 °C. After standing at 4 °C under its mother liquid within 24 hours a first‐order phase transition of 2a occurs forming dark blue prismatic single crystals of 2b . According to single crystal X‐ray structure determinations, 2a and 2b crystallize in the same type of space group , however, with different lattice dimensions. The vanadium(IV) complex 1 is characterized by X‐ray structure determination and by vibrational spectroscopy (IR, Raman) as well as by EPR spectroscopy, whereas 2b is characterized by IR spectroscopy. 1 : Space group P2₁/n, Z = 2, a = 1009.5(1), b = 1226.6(2), c = 1943.0(2) pm, β = 98.42(1)°, R₁ = 0.0672. The complex anion forms centrosymmetric units with V₂N₂‐four‐membered rings with a V···V distance of 335.6(1) pm and coordination number five on the vanadium(IV) atoms. 2a : Space group , Z = 1, a = 1089.0(2), b = 1097.1(2), c = 1310.1(2) pm, α = 92.99(1)°, β = 106.12(2)°, γ = 117.05(2)°, V = 1309.8(4) ų, d_calc. = 1.440 g·cm^?3, R₁ = 0.0384. The complex anion forms centrosymmetric units of symmetry C_i with V₂N₂ four‐membered rings and VN bond lengths of 200.4(3) and 234.4(2) pm, respectively. The non‐bonding V···V distance amounts to 356.2(1) pm. 2b : Space group , Z = 1, a = 1037.3(2), b = 1157.6(2), c = 1177.2(2) pm, α = 98.48(2)°, ° = 103.82(2)°, γ = 106.33(2)°, V = 1281.8(4) ų, d_calc. = 1.471 g·cm^?3, R₁ = 0.0724. The structure of the complex anion is similar to the anion of 2a with VN bond lengths of the four‐membered V₂N₂ ring of 203.3(4) and 235.2(4) pm, respectively, and a non‐bonding V···V distance of 357.5(1) pm.     

Die Reaktion von Ph3AsCl2 mit Acetonitril. Kristallstrukturen von [Ph3AsNC(Me)C(AsPh3)CN]+Cl– und des Palladium‐Molekülkomplexes [Ph3AsNC(Me)C(AsPh3)CN–PdCl3]

The Reaction of Ph₃AsCl₂ with Acetonitrile. Crystal Structures of [Ph₃AsNC(Me)C(AsPh₃)CN]⁺Cl^– and of the Palladium Molecular Complex [Ph₃AsNC(Me)C(AsPh₃)CN–PdCl₃] In the presence of potassium hydride the reaction of Ph₃AsCl₂ with acetonitrile leads to [Ph₃AsNC(Me) · C(AsPh₃)CN]⁺Cl^– ( 1 ), which is characterized by its infrared spectrum and by a crystal structure analysis. 1 can be explained as an insertion reaction of acetonitrile into an ylidic As–C bond of the primarily formed [(Ph₃As)₂CCN]Cl. 1 : Space group P1, Z = 2, lattice dimensions at –70 °C: a = 991.9(1), b = 1255.2(1), c = 1381.3(1) pm, α = 81.64(1)°, β = 80.12(1)°, γ = 78.17(1)°; R₁ = 0.051. 1 reacts with palladium(II) chloride to give the molecular complex [Ph₃AsNC(Me)C(AsPh₃)CN–PdCl₃] ( 2 ) with zwitterionic structure. The fragment {PdCl₃^–} is terminally bonded at the nitrogen atom of the CCN group of the cation of 1 in a linear arrangement CCNPd. 2 · CH₃CN: Space group P2₁, Z = 2, lattice dimensions at –90 °C: a = 1079.2(1), b = 1261.5(1), c = 1560.9(1) pm; β = 110.20(1)°; R₁ = 0.0283.     

Lanthanide(II) Complexes of the Dihydrotriazinido Ligand [N{C(Ph)=N}2C(tBu)Ph]−

The potassium dihydrotriazinide K(L^Ph,tBu) ( 1 ) was obtained by a metal exchange route from [Li(L^Ph,tBu)(THF)₃] and KOtBu (L^Ph,tBu = [N{C(Ph)=N}₂C(tBu)Ph]). Reaction of 1 with 1 or 0.5 equivalents of SmI₂(thf)₂ yielded the monosubstituted Sm^II complex [Sm(L^Ph,tBu)I(THF)₄] ( 2 ) or the disubstituted [Sm(L^Ph,tBu)₂(THF)₂] ( 3 ), respectively. Attempted synthesis of a heteroleptic Sm^II amido‐alkyl complex by the reaction of 2 with KCH₂Ph produced compound 3 due to ligand redistribution. The Yb^II bis(dihydrotriazinide) [Yb(L^Ph,tBu)₂(THF)₂] ( 4 ) was isolated from the 1:1 reaction of YbI₂(THF)₂ and 1 . Molecular structures of the crystalline compounds 2 , 3· 2C₆H₆ and 4· PhMe were determined by X‐ray crystallography.     

Higher α‐olefin polymerizations catalyzed by rac‐Me2Si(1‐C5H2‐2‐CH3‐4‐tBu)2Zr(NMe2)2/Al(iBu)3/[Ph3C][B(C6F5)4]

Polymerizations of higher α‐olefins, 1‐pentene, 1‐hexene, 1‐octene, and 1‐decene were carried out at 30 °C in toluene by using highly isospecific rac‐Me₂Si(1‐C₅H₂‐2‐CH₃‐4‐^t Bu)₂Zr(NMe₂)₂ (rac‐1) compound in the presence of Al(iBu)₃/[CPh₃][B(C₆F₅)₄] as a cocatalyst formulation. Both the bulkiness of monomer and the lateral size of polymer influenced the activity of polymerization. The larger lateral of polymer chain opens the π‐ligand of active site wide and favors the insertion of monomer, while the large size of monomer inserts itself into polymer chain more difficultly due to the steric hindrance. Highly isotactic poly(α‐olefin)s of high molecular weight (MW) were produced. The MW decreased from polypropylene to poly(1‐hexene), and then increased from poly(1‐hexene) to poly(1‐decene). The isotacticity (as [mm] triad) of the polymer decreased with the increased lateral size in the order: poly(1‐pentene) > poly(1‐hexene) > poly(1‐octene) > poly(1‐decene). The similar dependence of the lateral size on the melting point of polymer was recorded by differential scanning calorimetry (DSC). ¹H NMR analysis showed that vinylidene group resulting from β‐H elimination and saturated methyl groups resulting from chain transfer to cocatalyst are the main end groups of polymer chain. The vinylidene and internal double bonds are also identified by Raman spectroscopy. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1687–1697, 2000     

A Triple Cluster Platinaborane：[（P（2）Ph3）Pt（1）（μ2—B（11）—B（9）—OC（CH3）3—B10H10））Pt（7）（P（1）Ph3）]2

Ｉｎｒｅｃｅｎｔｙｅａｒｓｓｙｎｔｈｅｓｉｓａｎｄｃｈａｒａｃｔｅｒｉｚａｔｉｏｎｏｆｎｅｗｍｅｔａｌｌａｂｏｒａｎｅｓａｎｄｍｅｔａｌｌａｃａｒｂｏｒａｎｅｓｈａｖｅａｔｔｒａｃｔｅｄｍｕｃｈｉｎｔｅｒｅｓｔ .1 3Ａｗｉｄｅｖａｒｉｅｔｙｏｆｃｌｕｓｔｅｒｃｏｍｐｌｅｘｅｓ ,ｉｎｗｈｉｃｈｃｏｏｒｄｉｎａｔｉｏｎｃａｎｂｅｖｉａＢ—Ｈ—Ｍｏｒ (ａｎｄ)Ｂｎ—Ｍｂｏｎｄ(ｎ =1,2 ,3,4 ,5 ,6 ) ,ｈａｖｅｂｅｅｎｓｙｎｔｈｅｓｉｚｅｄａｎｄｓｔｒｕｃｔｕｒａｌｌｙｃｈａｒａｃｔｅｒｉｚｅｄ .Ｔｈｅｐｏ…     

Crystallographic report: Dimeric tetraphenyl‐1‐hydroxo‐3‐trifluoromethanesulfonatodistannoxane, [Ph2(HO)SnOSn(O3SCF3)Ph2]2

The molecular structure of the title compound, obtained by an adventitious phenyl group cleavage of Ph₃SnOSnPh₃ with triflic acid, reveals discrete centrosymmetric units of [Ph₂(HO)SnOSn(O₃SCF₃)Ph₂]₂ that are loosely associated via hydrogen bonding. Copyright © 2004 John Wiley & Sons, Ltd.     

The Reactions of Sodium Silanethiolates with Benzoyl Chloride. The Crystal Structures of (O‐silyl)thiobenzoates (tBuO)3SiOC(S)Ph,Ph3SiOC(S)Ph, (2,6‐XyO)3SiOC(S)Ph,and of PhC(O)SSSC(O)Ph

Benzoyl chloride reacts with sodium silanothiolates R₃SiSNa yielding exclusively silyl derivatives of thionobenzoic acid R₃SiOC(S)Ph, R = ^tBuO ( 1 ), R = Ph ( 2 ) and R = 2,6‐XyO ( 3 ) as orange solids. Compounds 1 , 2 , and 3 were fully characterized on the basis of X‐ray crystal structure analysis. NMR studies of solutions indicate that the same isomers are present in solutions and in solids.     

Mass spectra of 17ξ-hydroxy-5ξ-androstane C(3) ketone and C(3ξ) alcohol isomers

Positive ion electron impact mass spectral data for the four isomeric 17ξ-hydroxy-17ξ-methyl-5ξ-androstane C(3) ketones and the eight isomeric C(3ξ) alcohols are reported. In contrast to earlier reports, no general correlation was observed between the [M? H₂O]⁺˙/[M]⁺˙ ratio and the configuration at C(17). The ratios of the intensity of several fragment ions to that of the molecular ion do differentiate between the 5α- and 5β-isomers in both C(3) ketones and alcohols, the extent of fragmentation being greater for 5β-steroids. All of these fragments probably involve elimination of a water molecule at some stage in their formation. Elimination of water is also enhanced for 3α- v. 3β-hydroxysteroids, particularly in a 5β-isomer.     

Amide (A)–thioamide (T) interconversions using Ph3SiSH (A to T) and Ph3SnOH (T to A) reagents

Ph₃SiSH transforms amides to thioamides and Ph₃SnOH performs the reverse process, with the concomitant formation of Ph₃SiOH (or Ph₃SiOSiPh₃) and Ph₃SnSSnPh₃, respectively. The chemistry is a delightful illustration of the oxophilicity of silicon compared to the thiophilicity of tin and occurs under relatively mild conditions, and for amide to thioamide transformation requires no amide activation. The chemistry is in accord with available data for Si? (S)(O), Sn? (O)(S) and C?(O)(S) bond energies. Copyright © 2016 John Wiley & Sons, Ltd.     

(Ph2N)2Sm(THF)4与偶氮苯的反应：[(Ph2N)(DME)Sm]2(μ-η2:η2-N2Ph2)2的合成、X－光结构和催化行为

Reaction of divalent (Ph2N)2Sm(THF)4 with 1 equiv, of azobenzene in THF and then crystallization of the product in DME-Et2O mixed solvent produced the complex of [(PhEN)(DME)Sm]E(μ-η^2:η^2-N2Ph2)2 (1) in 65.0% yield. In complex 1, azobenzene molecules were reduced to be dianionic Ph2N2^2- ligands, bridging two samarium ions in two η^2:η^2 fashions. One samarium ion was bonded to a DME molecule and a diphenyl amido ligand besides two Ph2N2^2- ligands. The unusual Ln-η^2-arene close interaction was found for the first time for diphenyl amido lanthanides. Complex 1 could catalyze the polymerization of methyl methacrylate and acrylonitrile