Syntheses,Crystal Structures and Non‐linear Optical Properties of Cluster Compounds [MoAu2S4(PPh2Py)2] and [WAu2S4(PPh2Py)2]

The cluster compounds, [MoAu₂S₄(PPh₂Py)₂] ( 1 ) and [WAu₂S₄(PPh₂Py)₂] ( 2 ), were synthesized by the reaction of (NH₄)₂MS₄ (M = Mo, W), H[AuCl₄]·4H₂O and diphenyl‐2‐pyridyl‐phosphine (PPh₂Py) in CH₂Cl₂ solution. [MoAu₂S₄(PPh₂Py)₂] crystallizes in the monoclinic space group P2₁/c with a = 18.385(2), b =12.304(1), c = 16.904(2) Å, β =110.722(2)°, and Z = 4. [WAu₂S₄(PPh₂Py)₂] crystallizes in the triclinic space group P‐1 with a = 9.333 (3), b = 10.628(3), c = 19.566(6) Å, α = 89.26(1), β = 80.87(1), γ = 68.85(1)°, and Z = 2. Single crystal X‐ray analysis showed that these two compounds are isostructural, but belong to different space groups. The Mo (W) atom has a slightly distorted tetrahedral coordination, and the two Au atoms are distorted from trigonal planar, the P—Au—M—Au—P chain is nearly linear. Measurement of the nonlinear optical (NLO) properties using the Z‐scan technique with an 8‐ns pulsed laser at 532 nm showed that 1 and 2 possess NLO absorption and effective self‐focusing effect. The effective α₂ and n₂ values of cluster 1 are 5.89 × 10^—12 m · W^—1 and 6.45 × 10^—18 m² · W^—1; the effective α₂ and n₂ values of compound 2 are 4.35 × 10^—11 m · W^—1 and 3.73 × 10^—17 m² · W^—1.     

Rational synthesis, structural characterization and the third-order nonlinear optical properties of two new M-Cu-S (M = Mo or W) clusters

By the additional reaction of binuclear compounds (Me4N)2M2S4 (TDT)2 (M = Mo, W; H2TDT= H2CH3C6H3S2) with mononuclear cuprous complex, two new M-Cu-S clusters Mo2Cu2S4(TDT)2-(PPh3 )2·CH3CH2OH (1) and W2Cu2S4(TDT)2(PPh3)2·0.5CH3CH2OH-0.5H2O (2) have been prepared and characterized by IR, UV-Vis, 31P NMR spectroscopy, cyclic voltammetry and single crystal X-ray structure analysis . Both compounds crystallize in space group P 21 / n with lattice parameters a = 1.0956(3), b = 2.2072(3), c = 2.4340(3) nm, β= 100.36(2)°, V= 5.790(3) nm3 and Z = 4 for 1 and a = 1.0965(9),b= 2.2135(3), c = 2.4317(4) nm, β = 99.63(8)°, V= 5.819(8) nm3 and Z = 4 for 2. Both molecular structures contain a cubane-like cluster core [M2Cu2S4] (M = Mo, W) and their skeletons are almost the same except for M atoms. The syntheses, structures and spectrum characterizations of these two clusters are discussed. The third-order nonlinear optical (NLO) property of the two clusters was studied by the technique of forward degenerate four     

Synthesis and crystal structure of [W3S4(Acac)3(PPh3)3]PF6 · 0.5CHCl3 and [W3S4(Hfac)3(PPh3)2Br] · 2CHCl3

New cluster complexes [W₃S₄(Acac)₃(PPh₃)₃]PF₆ · 0.5CHCl₃ (Acac = CH₃C(O)CHC(O)CH₃) (I) and [W₃S₄(Hfac)₃(PPh₃)₂Br] · 2CHCl₃ (Hfac = CF₃C(O)CHC(O)CF₃) (II) were synthesized. Their molecular and crystal structures were determined by X-ray diffraction. The cis-cis type of coordination of acetylacetonate and hexafluoroacetylacetonate ligands in I and II, respectively, was established, and the PPh₃ ligands were found in the trans-positions with respect to the “capping” sulfide ligand (μ³-S).     

New Bimetallics of Mo and W with Metallocene,Metal Carbonyl and Bridging PPh2 or ‘Cp’PPh2 Units

Ring substituted (R=^tBu, SiMe₃) metallocene dichlorides undergo a nucleophilic substitution on one of the two rings upon the action of LiPPh₂M'(CO)_x salts with the formation of chloro-hydrido complexes [C₅H₃(R)PPh₂M'(CO)_x](C₅H₄R)M(H)Cl. Their UV irradiation leads to the chloro-bridged M(μ-Cl)M' separable diastereoisomers. Use of the ansa-metal-locene dichlorides [Me₂X(C₅H₄)₂MCl₂] (X=Si or C) allowed the access to the new bridging system [M(μ-PPh₂, μ-Cl)M′] (M=Mo, W ; M'=W).     

Synthesis and structural characterization of ruthenium complexes with 1-aryl-imidazole-2-thione

Treatment of [RuCl₂(PPh₃)₃] with 2 equiv. Himt^MPh (Himt^MPh?=?1-(4-methyl-phenyl)-imidazole-2-thione) in the presence of MeONa afforded cis-[Ru(κ ²-S,N-imt^MPh)₂(PPh₃)₂] (1), while interaction of [RuCl₂(PPh₃)₃] and 2 equiv. Himt^MPh in tetrahydrofuran (THF) without base gave [RuCl₂(κ ¹-S-Himt^MPh)₂(PPh₃)₂] (2). Treatment of [RuHCl(CO)(PPh₃)₃] with 1 equiv. Himt^MPh in THF gave [RuHCl(κ ¹-S-Himt^MPh)(CO)(PPh₃)₂] (3), whereas reaction of [RuHCl(CO)(PPh₃)₃] with 1 equiv. of the deprotonated [imt^MPh]^? or [imt^NPh]^? (imt^NPh?=?1-(4-nitro-phenyl)-2-mercaptoimidazolyl) gave [RuH(κ ²-S,N-imt^RPh)(CO)(PPh₃)₂] (R?=?M 4a, R?=?N 4b). The ruthenium hydride complexes 4a and 4b easily convert to their corresponding ruthenium chloride complexes [RuCl(κ ²-S,N-imt^MPh)(CO)(PPh₃)₂] (5a) and [RuCl(κ ²-S,N-imt^NPh)(CO)(PPh₃)₂] (5b), respectively, in refluxing CHCl₃ by chloride substitution of the RuH. Photolysis of 5a in CHCl₃ at room temperature afforded an oxidized product [RuCl₂(κ ²-S,N-imt^MPh)(PPh₃)₂] (6). Reaction of 6 with excess [imt^MPh]^? afforded 1. The molecular structures of 1·EtOH, 3·C₆H₁₄, 4b·0.25CH₃COCH₃, and 6·2CH₂Cl₂ have been determined by single-crystal X-ray crystallography.     

Synthesis and characterization of cyclometallated palladium(II) and platinum(II) complexes with amide-thiolate ligands

The redox reaction of bis(2-benzamidophenyl) disulfide (H₂L-LH₂) with [Pd(PPh₃)₄] in a 1:1 ratio gave mononuclear and dinuclear palladium(II) complexes with 2-benzamidobenzenethiolate (H₂L⁻), [Pd(H₂L-S)₂(PPh₃)₂] (1) and [Pd₂(H₂L-S)₂ (μ-H₂L-S)₂(PPh₃)₂] (2). A similar reaction with [Pt(PPh₃)₄] produced only the corresponding mononuclear platinum(II) complex, [Pt(H₂L-S)₂(PPh₃)₂] (3). Treatment of these complexes with KOH led to the formation of cyclometallated palladium(II) and platinum(II) complexes, [Pd(L-C,N,S)(PPh₃)]⁻ ([4]⁻) and [Pt(L-C,N,S) (PPh₃)]⁻ ([5]⁻). The molecular structures of 2, 3 and [4]⁻ were determined by X-ray crystallography.     

Effects on Coordination of Thioether Sites. 4. Structural Analysis of η3-Tripodal Ligand Manganese(I) Complexes

Crystal structures of a series of manganese(I) complexes containing tripodal ligands were determined. For [η³-{CH₃C(CH₂PPh₂)₂(CH₂SPh)-P,P′,S}Mn(CO)₃]PF₆ ( 1 ): a = 10.856(3) Å, b = 19.698(3) Å, c = 17.596(5) Å, β = 96.17(2)°, monoclinic, Z = 4, P2₁/c, R(F_o) = 0.068, R_w(F_o) = 0.055 for 3617 reflections with I_o > 2σ(I_o). For [η³-{CH₃C(CH₂PPh₂)(CH₂SPh)₂-P,P′,S}Mn(CO)₃]PF₆ ( 2 ): a = 9.890(2) Å, b = 20.403(4) Å, c = 10.269(3) Å, β = 117.44(2)°, monoclinic, Z = 2, P2_l, R(F_o) = 0.050, R_w(F_o) = 0.037 for 1760 reflections with I_o > 2σ(I_o). For [η³-{CH₃C(CH₂PPh₂)₂(CH₂S)-P,P′,S}Mn(CO)₃] ( 4 ): a = 8.191(7) Å, b = 10.495(3) Å, c = 19.858(6) Å, α = 99.61(2)°, β = 96.17(2)°, γ = 92.70(4)°, triclinic, Z = 2, P-I, R(F_o) = 0.048, R_w(F_o) = 0.039 for 2973 reflections with I_o > 2σ(I_o). There is no significant difference in the bond lengths of Mn-S bonds among three species in their crystal structures [2.325(2) Å in 1; 2.358(4) in 2; 2.380(2) in 4], but the better donating ability of thiolate in complex 4 appears on the lower frequencies of its carbonyl stretching absorptions.     

Synthese und Struktur des μ-Sulfido-μ-disulfido-octabromodiwolframat(V)-Ions [W2S3Br8]2−

Synthesis and Structure of μ-Sulfido-μ-disulfido-octabromoditungstate(V), [W₂S₃Br₈]^?2 Tungsten hexabromide reacts with H₂S in dichloromethane yielding a brown product which, by addition of tetraphenylphosphonium bromide in CH₂Cl₂, is converted to brown, crystalline (PPh₄)₂[Br₄W(μ-S)(μ-S₂)WBr₄] · CH₂Cl₂ · CH₂S. Its IR spectrum is reported, its crystal structure was determined by X-ray diffraction (2330 reflexions, R = 0.097). Crystal data: orthorhombic, Pnma, a = 1 766.5, b = 2 412.7, c = 1 416.3 pm, Z = 4. In the diamagnetic [W₂S₃Br₈]^2? ions the two W atoms are linked via a sulfido and a disulfido bridge and by a W? W bond.     

Reactions involving transition metals : XIX. Some reactions of perfluoronorbornadiene with low valent transition metal complexes

Perfluoronorbornadiene reacts with the compounds [M(PPh₃)₄] (M = Pt, Pd) and [IrCl(CO)(PMePh₂)₂] to give the adducts [(C₇F₈)M(PPh₃)₂] and [(C₇F₈)IrCl(CO)(PMePh₂)₂] in which one of the double bonds is coordinated to the metal atom. The platinum complex reacts further with [Pt(PPh₃)₄] to give [(C₇F₈){Pt(PPh₃)₂}₂] having both double bonds coordinated to a Pt atom. The carbonylmetal anions [M^?] react to form the mono-substitution products [(C₇F₇)M] (M = Mn(CO)₅, Re(CO)₅, Ir(CO)₂(PPh₃)₂, Rh(CO)₂(PPh₃)₂), but the use of an excess of [Fe(CO)₂(η-C₅H₆)]^? leads to substitution of one fluorine atom on each of the double bonds. The complex having M = Mn(CO)₅ reacts with [Pt(PPh₃)₄] to afford the derivative [(C₇F₇){Mn(CO)₄(PPh₃)}{Pt(PPh₃)₂}], and the compound where M = Ir(CO)₂(PPh₃)₂ undergoes an oxidative addition reaction with acetyl chloride. Oxidative coupling products have been isolated on UV irradiation of a mixture of perfluoronorbornadiene and [Fe(η⁴-CH₂CRCHCH₂)(CO)₃] (R = H, Me), and under similar conditions the reaction with Fe(CO)₅ affords [(C₇F₈)Fe(CO)₄] in very low yield.     

Reactions of cationic rhodium(I) carbonyl compounds with nucleophiles to form alkoxo,carboalkoxy and carboxylato complexes. Part II

Summary The rhodium(I) carbonyl compounds [Rh(CO)L₂2] [BF₄]. 1/2CH₂Cl_nn2 (L = PPh₂ or AsPh₃) react with the nucleophiles OMe⁻, RCOO⁻ (R = Me, Et) under nitrogen to form [Rh(OR)(CO)L₂] (1)–(2) and [Rh(OOCR)(CO)L₂] (7)–(₁₀), respectively. Addition of [Rh(CO)₂(PPh₃)₂]-[BF ₄] to OMe⁻ under nitrogen produces [Rh(COOMe)-(CO) (PPh₃)₂]-MeOH (3), whilst reactions of [Rh(CO)-(PPh₃)₂] [BF₄]·1/2CH₂Cl₂ and [Rh(CO)₂(PPh₃)₂] [BF₄] with OR_- (R = Me, Et or n-Pr) in the presence of CO produce [Rh(COOR)(CO)₂(PPh₃)₂] (4)–(6). The products have been characterised by i.r., ¹H, ³¹P, ¹³Cn.m.r. spectroscopy and elemental analysis.     

Metal/Metal Redox Isomerism Governed by Configuration

A pair of diastereomeric dinuclear complexes, [Tp′(CO)BrW{μ-η²-C,C′-κ²-S,P-C₂(PPh₂)S}Ru(η⁵-C₅H₅)(PPh₃)], in which W and Ru are bridged by a phosphinyl(thiolato)alkyne in a side-on carbon P,S-chelate coordination mode, were synthesized, separated and fully characterized. Even though the isomers are similar in their spectroscopic properties and redox potentials, the like-isomer is oxidized at W while the unlike-isomer is oxidized at Ru, which is proven by IR, NIR and EPR-spectroscopy supported by spectro-electrochemistry and computational methods. The second oxidation of the complexes was shown to take place at the metal left unaffected in the first redox step. Finally, the tipping point could be realized in the unlike isomer of the electronically tuned thiophenolate congener [Tp′(CO)(PhS)W{μ-η²-C,C′-κ²-S,P-C₂(PPh₂)S}Ru(η⁵-C₅H₅)-(PPh₃)], in which valence trapped W^III/Ru^II and W^II/Ru^III cationic species are at equilibrium.     

Oxorhenium(V) Complexes with 1,3,4‐Triphenyl‐1,2,4‐triazol‐5‐ylidene

Reactions of the oxorhenium(V) complexes [ReOX₃(PPh₃)₂] (X = Cl, Br) with the N‐heterocyclic carbene (NHC) 1,3,4‐triphenyl‐1,2,4‐triazol‐5‐ylidene (L^Ph) under mild conditions and in the presence of MeOH or water give [ReOX₂(Y)(PPh₃)(L^Ph)] complexes (X = Cl, Br; Y = OMe, OH). Attempted reactions of the carbene precursor 5‐methoxy‐1,3,4‐triphenyl‐4,5‐dihydro‐1H‐1,2,4‐triazole ( 1 ) with [ReOCl₃(PPh₃)₂] or [NBu₄][ReOCl₄] in boiling xylene resulted in protonation of the intermediately formed carbene and decomposition products such as [HL^Ph][ReOCl₄(OPPh₃)], [HL^Ph][ReOCl₄(OH₂)] or [HL^Ph][ReO₄] were isolated. The neutral [ReOX₂(Y)(PPh₃)(HL^Ph)] complexes are purple, airstable solids. The bulky NHC ligands coordinate monodentate and in cis‐position to PPh₃. The relatively long Re–C bond lengths of approximate 2.1Å indicate metal‐carbon single bonds.     

Phenylimido Complexes of Technetium and Rhenium with Maleonitriledithiolate

[Tc(NPh)Cl₃(PPh₃)₂] or [Re(NPh)Cl₃(PPh₃)₂] react with two equivalents of Na₂mnt (mnt^2– = 1,2‐dicyanoethene‐1,2‐dithiolate) with formation of anionic complexes of the composition [M(NPh)(mnt)₂]^–. The products can be isolated as large red blocks of their AsPh₄⁺ salts. The complex anions contain square‐pyramidal coordinated metal atoms with the phenylimido ligands in apical positions. The M–N–C bonds are almost linear. A similar phenylimido complex with an additional amino group was synthesized from [Re(NC₆H₄‐4‐NH₂)Cl₃(PPh₃)₂]. The presence of such substituents may allow coupling of the metal complexes to biomolecules such as peptides, proteins, or sugars, provided the M=N bonds are sufficiently stable against hydrolysis.     

Neue Phosphido-verbrückte Mehrkernkomplexe des Ag,Cd und Zn Die Kristallstrukturen von [Ag4(PPh2)4(PMe3)4], [Ag6(PPh2)6(PtBu3)2] und [M4Cl4(PPh2)4(PnPr3)2] (M = Zn,Cd)

New Phosphido-bridged Multinuclear Complexes of Ag, Cd and Zn. The Crystal Structures of [Ag₄(PPh₂)₄(PMe₃)₄], [Ag₆(PPh₂)₆(P^tBu₃)₂] and [M₄Cl₄(PPh₂)₄(PⁿPr₃)₂] (M = Zn, Cd) AgCl reacts with Ph₂PSiMe₃ in the presence of a tertiary Phosphine PMe₃ or P^tBu₃ to form the multinuclear complexes [Ag₄(PPh₂)₄(PMe₃)₄] ( 1 ) and [Ag₆(PPh₂)₆(P^tBu₃)₂] ( 2 ). In analogy to that MCl₂ reacts with Ph₂PSiMe₃ in the presence of PⁿPr₃ to form the two multinuclear complexes [M₄Cl₄(PPh₂)₄(PⁿPr₃)₂] (M = Zn ( 3 ), Cd ( 4 )). The structures were characterized by X-ray single crystal structure analysis ( 1 : space group Pna2₁ (Nr. 33), Z = 4, a = 1 313.8(11) pm, b = 1 511.1(6) pm, c = 4 126.0(18) pm, 2 : space group P–1 (Nr. 2), Z = 2, a = 1 559.0(4) pm, b = 1 885.9(7) pm, c = 2 112.4(8) pm, α = 104.93(3)°, β = 94.48(3)°, γ = 104.41(3)°; 3 : space group C2/c (Nr. 15), Z = 4, a = 2 228.6(6) pm, b = 1 847.6(6) pm, c = 1 827.3(6) pm, β = 110.86(2); 4 : space group C2/c (Nr. 15), Z = 4, a = 1 894.2(9) pm, b = 1 867.9(7) pm, c = 2 264.8(6) pm, β = 111.77(3)°). 3 and 4 may be considered as intermediates on the route towards polymeric [M(PPh₂)₂]_n (M = Zn, Cd).     

Synthesen und Strukturen von Übergangsmetall‐Komplexen mit Dithiophosphinato‐ und Trithiophosphonato‐Liganden

Syntheses and Structures of Transition Metal Complexes with Dithiophosphinato and Trithiophosphinato Ligands The reactions of MnCl₂ with Ph₂P(S)(SSiMe₃) produced [Mn(S₂PPh₂)₂(thf)₂] ( 1 ) and [Mn(S₂PPh₂)₂(dme)] ( 2 ) (DME = 1,2‐Dimethoxyethane). The compounds [Co₆(S₃PPh)₂(μ⁴‐S)₂(μ³‐S)₂(PPh₃)₄] ( 3 ), [Co₂(S₃PPh)₂(PPh₃)₂] ( 4 ), [Ni(S₂PPh)(PPhEt₂)₂] ( 5 ), [Ni(S₃PPh)(PPhEt₂)₂] ( 6 ) and [Cu₄(S₃PPh)₂(dppp)₂] ( 8 ) [dppp = 1,3‐Bis(diphenylphosphanyl)propane] were obtained from reactions of first‐row transition metal halides with PhP(S)(SSiMe₃)₂ in the presence of tertiary phosphines. In a reaction of PhP(S)(SSiMe₃)₂ with PhPEt₂ PhPEt₂PS₂Ph ( 7 ) was isolated. All compounds were characterized by X‐ray crystallography.     

Synthesis, Structure, and 31P NMR of Sulfur/Oxygen-Bridged Incomplete Cubane-Type Molybdenum and Tungsten Clusters with Triphenylphosphine Ligands

Sulfur/oxygen-bridged incomplete cubane-type triphenylphosphine molybdenum and tungsten-clusters [Mo₃S₄Cl₄(H₂O)₂(PPh₃)₃]·3THF (1A), [Mo₃S₄Cl₄(H₂O)₂(PPh₃)₃]·2THF (2A), [Mo₃OS₃Cl₄(H₂O)₂(PPh₃)₃]·2THF (1B), and [W₃S₄Cl₄(H₂O)₂(PPh₃)₃]·2THF (1C) were prepared from the corresponding aqua clusters and PPh₃ in THF/MeOH. On recrystallization from THF, procedures with and without addition of hexane to the solution gave 1A and 2A, respectively, while the procedures gave no effect on the formation of 1B and 1C. Crystallographic results obtained are as follows: 1A: monoclinic, P2₁/n, a=17.141(4) Å, b=22.579(5) Å, c=19.069(4) Å, =96.18(2)°, V=7337(3) ų, Z=4, R(R _w)=0.078(0.102); 1C: monoclinic, P2 ₁/c, a=12.635(1) Å, b=20.216(4) Å, c=27.815(3) Å, =96.16(1)°, V=7062(2) ų, Z=4, R(R _w)=0.071(0.083). If the phenyl groups are ignored, the molecule [Mo₃S₄Cl₄(H₂O)₂(PPh₃)₃] in 2A has idealized CS symmetry with the mirror plane perpendicular to the plane determined by the metal atoms, while the molecule in 1A does not have the symmetry. The tungsten compound 1C is isomorphous with the molybdenum compound 2A. ³¹P NMR spectra of 1A, 2A, and 1C were obtained and compared with similar clusters with dmpe (1,2-bis(dimethylphosphino)ethane) ligands.     

m‐Metallaphenol: Synthesis and Reactivity Studies

Treatment of the osmium complex [Os{CHC‐(PPh₃)CH(OH)‐η²‐C≡CH}(PPh₃)₂(NCS)₂] ( 1 ) with excess triethylamine produces the first m‐metallaphenol complex [Os{CHC(PPh₃)CHC(OH)CH}(PPh₃)₂(NCS)₂] ( 2 ). The NMR spectroscopic and structural data as well as the nucleus‐independent chemical‐shift (NICS) values suggest that osmaphenol 2 has aromatic character. The reactivity studies demonstrate that 2 can react with different isocyanates to form the annulation reaction products [Os{CHC(PPh₃)CHC(O?C?ONR)C}(PPh₃)₂(NCS)₂] (R=Ph ( 3 ), iPr ( 7 ), Bn ( 8 )) via the carbamate intermediates [Os{CHC(PPh₃)CHC(O‐C?ONHR)CH}(PPh₃)₂(NCS)₂] (R=Ph ( 4 ), iPr ( 5 ), Bn ( 6 )). In addition, the similar annulation reactions can be extended to other unsaturated compounds containing N–C multiple bonds, for example, isothiocyanates, pyridine, and sodium thiocyanate, which can produce the corresponding fused osmabenzene complexes. In contrast, the reactions of 2 with common electrophiles, such as NOBF₄, NO₂BF₄, N‐bromosuccinimide, and N‐chlorosuccinimide only led to the decomposition of the metallaphenol ring. The experimental results suggest that 2 is very electrophilic and readily reacts with nucleophiles, which is mainly due to the metal center and the strong electron‐withdrawing phosphonium group.     

Addition von kationischen Lewis‐Säuren [M′Ln]+ (M′Ln = Fe(CO)2Cp,Fe(CO)(PPh3)Cp,Ru(PPh3)2Cp,Re(CO)5, ${1 \over 2}$ Pt(PPh3)2, W(CO)3Cp an die anionischen Thiocarbonyl‐Komplexe [HB(pz)3(OC)2M(CS)]− (M = Mo,W; pz = 3,5‐dimethylpyrazol‐1‐yl)

Addition of Cationic Lewis Acids [M′L_n]⁺ (M′L_n = Fe(CO)₂Cp, Fe(CO)(PPh₃)Cp, Ru(PPh₃)₂Cp, Re(CO)₅, Pt(PPh₃)₂, W(CO)₃Cp to the Anionic Thiocarbonyl Complexes [HB(pz)₃(OC)₂M(CS)]⁻ (M = Mo, W; pz = 3,5‐dimethylpyrazol‐1‐yl) Adducts from Organometallic Lewis Acids [Fe(CO)₂Cp]⁺, [Fe(CO)(PPh₃)Cp]⁺, [Ru(PPh₃)₂Cp]⁺, [Re(CO)₅]⁺, [ Pt(PPh₃)₂]⁺, [W(CO)₃Cp]⁺ and the anionic thiocarbonyl complexes [HB(pz)₃(OC)₂M(CS)]⁻ (M = Mo, W) have been prepared. Their spectroscopic data indicate that the addition of the cations occurs at the sulphur atom to give end‐to‐end thiocarbonyl bridged complexes [HB(pz)₃(OC)₂MCSM′L_n].     

Reaktionen von Zinnchloriden mit Polysulfiden. Die Kristallstrukturen von (PPh4)2[SnCl2(S6)2], (PPh4)2[Sn4Cl4S5(S3)O] und (PPh4)2[SnCl6] · S8 · 2CH3CN

Reaction of Tin Chlorides with Polysulfides. Crystal Structures of (PPh₄)₂[SnCl₂(S₆)₂], (PPh₄)₂[Sn₄Cl₄S₅(S₃)O], and (PPh₄)₂[SnCl₆] · S₈ · 2CH₃CN . The reaction of PPh₄[SnCl₃] with Na₂S₄ in acetonitrile in the presence of small amounts of water yields (PPh₄)₂[Sn₄Cl₄S₅(S₃)O] and minor amounts of (PPh₄)₂[SnCl₂(S₆)₂], PPh₄Cl · 2S₈ and (PPh₄)₂[SnCl₆]. SnCl₄ is partially reduced by (PPh₄)₂S_x, PPh₄[SnCl₃] and (PPh₄)₂[SnCl₆] · S₈ · 2CH₃CN being produced. According to the X-ray crystal structure determination the [Sn₄Cl₄S₅(S₃)O]^2?-ion consists of an O atom that is coordinated by four Sn atoms which in turn are liked with one another by five single S atoms and one S₃ group. In the [SnCl₂(S₆)₂]^2?-ion the Sn atom is octahedrally coordinated by two Cl atoms in trans arrangement and by two chelating S₆ groups. Octahedral [SnCl₆]^2? ions and S₈ molecules in the crown conformation are present in (PPh₄)₄[SnCl₆] · S₈ · 2CH₃CN.     

Synthesis,Spectroscopy, and Structures of Mono‐ and Dinuclear Copper(I) Halide Complexes with 1,3‐Imidazolidine‐2‐thiones

Copper(I) halides with triphenyl phosphine and imidaozlidine‐2‐thiones (L ‐NMe, L ‐NEt, and L ‐NPh) in acetonitrile/methanol (or dichloromethane) yielded copper(I) mixed‐ligand complexes: mononuclear, namely, [CuCl(κ¹‐S‐L ‐NMe)(PPh₃)₂] ( 1 ), [CuBr(κ¹‐S‐L ‐NMe)(PPh₃)₂] ( 2 ), [CuBr(κ¹‐S‐L ‐NEt)(PPh₃)₂] ( 5 ), [CuI(κ¹‐S‐L ‐NEt)(PPh₃)₂] ( 6 ), [CuCl(κ¹‐S‐L ‐NPh)(PPh₃)₂] ( 7 ), and [CuBr(κ¹‐S‐L ‐NPh)(PPh₃)₂] ( 8 ), and dinuclear, [Cu₂(κ¹‐I)₂(μ‐S‐L ‐NMe)₂(PPh₃)₂] ( 3 ) and [Cu₂(μ‐Cl)₂(κ¹‐S‐L ‐NEt)₂(PPh₃)₂] ( 4 ). All complexes were characterized with analytical data, IR and NMR spectroscopy, and X‐ray crystallography. Complexes 2 – 4 , 7 , and 8 each formed crystals in the triclinic system with P$\bar{1}$ space group, whereas complexes 1 , 5 , and 6 crystallized in the monoclinic crystal system with space groups P2₁/c, C2/c, and P2₁/n, respectively. Complex 2 has shown two independent molecules, [(CuBr(κ¹‐S‐L ‐NMe)(PPh₃)₂] and [CuBr(PPh₃)₂] in the unit cell. For X = Cl, the thio‐ligand bonded to metal as terminal in complex 4 , whereas for X = I it is sulfur‐bridged in complex 3 .