An Unusual Product from the Reaction of C(PPh3)2 with [Mn2(CO)10]: Formation and Crystal Structure of [Mn(OPPh3)2{O2CC(PPh3)2}2][Mn(CO)5]2

The carbodiphosphorane C(PPh₃)₂ ( 1 ) reacts with [Mn₂(CO)₁₀] in THF to produce quantitatively the salt‐like complex (HC{PPh₃}₂)[Mn(CO)₅] ( 2 ) as THF solvate. If the reaction is carried out in 1,2‐dimethoxyethane (DME) small amounts of [Mn(OPPh₃)₂{O₂CC(PPh₃)₂}₂][Mn(CO)₅]₂ ( 3 ) as DME solvate along with solvent free 2 as the main product were isolated. Proton abstraction from the solvent led to the formation of 2 ; the ligands OPPh₃ and O₂CC(PPh₃)₂}₂ of 3 are the results of a side reaction from [Mn₂(CO)₁₀] and 1 in a Wittig type manner. From the reaction in benzene small amounts of 3 were also obtained, crystallizing as benzene solvate 3· 4C₆H₆. The crystal structures of 2· THF, 2 , 3· 1.75DME and 3· 4C₆H₆ are reported. The compounds are further characterized by IR and ³¹P NMR spectroscopy.     

Formation of the Salt‐like Complexes [Co{S2CC(PPh3)2}3][Co(CO)4]3 and [(CO)4Mn{S2CC(PPh3)2}][Mn(CO)5] from the Reaction of the Related Carbonyl Compounds with S2CC(PPh3)2

The betain‐like compound S₂CC(PPh₃)₂ ( 1 ), which is obtained from CS₂ and the double ylide C(PPh₃)₂, reacts with [Co₂(CO)₈] and [Mn₂(CO)₁₀] in THF to afford the salt‐like complexes [Co{S₂CC(PPh₃)₂}₃][Co(CO)₄]₃ ( 2 ) and [(CO)₄Mn{S₂CC(PPh₃)₂}][Mn(CO)₅] ( 3 ), respectively, in good yields. At both d⁶ cations 1 acts as a chelating ligand. Disproportionation reactions from formal Co⁰ into Co^III and Co^?I and from Mn⁰ into Mn^I and Mn^?I occurred with the removal of four or one carbonyl groups, respectively. The crystal structures of 2· 5.5THF and 3· 2THF are reported, which show a shortening of the C–C bond in the ligand upon complex formation. The compounds are further characterized by ³¹P NMR and IR spectroscopy.     

[(Te2)3{Mn(CO)3}2{Mn(CO)4}3]– – A Novel Tellurium‐­Manganese Carbonyl with Ufosane‐like Structure

By reacting Mn₂(CO)₁₀ and TeI₄ in the ionic liquid[BMIm][OTf] (1‐butyl‐3‐methylimidazolium trifluromethanesulfonate), brick‐red crystals of [BMIm][(Te₂)₃{Mn(CO)₃}₂{Mn(CO)₄}₃]are obtained. The title compound contains the carbonyl anion[(Te₂)₃{Mn(CO)₃}₂{Mn(CO)₄}₃]^–. Herein, three formal Te₂^2– units and two formal Mn(CO)₃⁺ fragments establish a distorted heterocubane‐like Te₆Mn₂ structure. Three edges of this heterocubane are furthermore capped by Mn(CO)₄⁺ fragments. The resulting Te₆Mn₅ building unit, moreover, looks very similar to the P₁₁^3– anion – the so‐called ufosane. The mean distances Te–Te and Te–Mn are observed with 277.6 and 264.7 pm, respectively. In addition to single‐crystal structure analysis, the title compound is characterized by infrared spectroscopy (FT‐IR), thermogravimetry (TG) and energy‐dispersive X‐ray (EDX) analysis.     

Synthesis of bridged and linked ruthenium and osmium carbonyl clusters containing a [Au2(Ph2PCH2CH2PPh2)]2+ unit. The crystal and molecular structures of Ru5C(CO)14Au2(Ph2PCH2CH2PPh2) and {Os4H3(CO)12}2Au2(Ph2PCH2CH2PPh2)

Treatment of Au₂(Ph₂PCH₂CH₂PPh₂)Cl₂ with one equivalent of the [Ru₅C(CO)₁₄]²⁻ dianion in the presence of TlPF₆ gives Ru₅C(CO)₁₄Au₂(Ph₂PCH₂CH₂PPh₂) (1) in good yield and the [{Ru₅C(CO)₁₄}₂Au₂(Ph₂PCH₂CH₂PPh₂)]²⁻ (2) anion in low yield. Complex 2 becomes the major product if 2 equivalents of [Ru₅C(CO)₁₄]²⁻ are used. Reaction of [Au₂(Ph₂PCH₂CH₂PPh₂)Cl₂] with 3 equivalents of [H₃Os₄(CO)₁₂]⁻ anion in the presence of TlPF₆ affords {H₃Os₄(CO)₁₂}₂Au₂(Ph₂PCH₂CH₂PPh₂) (3) in reasonable yield. X-ray diffraction studies of 1 and 3 show that they contain the [Au₂(Ph₂PCH₂CH₂PPh₂)]²⁺ fragment in different coordination modes.     

Die Bildung von PPh4[WOCl4 · THF] und PPh4Cl · 4As4S3 aus W(CO)6 und PPh4[As2SCl5] sowie ihre Kristallstrukturen

Formation of PPh₄[WOCl₄ · THF] and PPh₄Cl · 4As₄S₃ from W(CO)₆ and PPh₄[As₂SCl₅] and their Crystal Structures When W(CO)₆ and PPh₄[As₂SCl₅] are irradiated with UV light in tetrahydrofurane, PPh₄[WOCl₄ · THF], PPh₄ Cl· 4As₄S₃ and PPh₄[Cl₂H] are obtained. X-ray crystal structure determinations were performed. PPh₄[WOCl₄ · THF], monoclinic, space group P2₁/c, Z = 4, a = 1207.5(2), b = 1003.7(2), c = 2642.0(5) pm, β = 114.71(1)°, R = 0.049% for 2824 reflexions; PPh₄⁺ and [WOCl₄. THF]^? ions are present, the WOCl₄ group having the shape of a tetragonal Pyramid with a short W ? O bond (169 pm) and the THF molecule being weakly associated (W? O 236 pm). PPh₄Cl · 4AsS₃, tetragonal, I4₁/a, Z = 4, a = 1742.3(3), c = 1664.5(4) pm, R = 0.066% for 1350 reflexions; it consists of separate PPh₄⁺ and Cl^? ions and As₄S₃ molecules.     

THE REACTIONS OF [MoCl(GeCl3)(CO)3(NCMe)2] WITH NEUTRAL BI- AND TERDENTATE DONOR LIGANDS

Abstract

The reaction of [MoCl(GeCl₃)(CO)₃(NCMe)₂] with an equimolar quantity of L?L {L?L = 2,2′-bipy, 1,10-phen, Ph₂P(CH₂)_nPPh₂ (n = 1 or 2)} in CH₂Cl₂ at room temperature gave either [MoCl(GeCl₃)(CO)₃(L?L)] (L?L = 2,2′-bipy or 1,10-phen) (1 and 2) or [MoCl(GeCl₃)(CO)₂ (NCMe)(L?L)]{L?L = Ph₂P(CH₂)_nPPh₂ (n = 1 or 2) (3 or 4), respectively. Equimolar quantities of [MoCl(GeCl₃)(CO)₂(NCMe){Ph₂P(CH₂)PPh₂}] (3) and L?L {L?L = 2,2′-bipy or Ph₂P(CH)₂PPh₂} react in CH₂Cl₂ at room temperature to afford the cationic complexes [Mo(GeCl₃)(CO)₂{Ph₂P(CH₂) PPh₂}(L?L)]Cl (5 and 6) in good yield. The cationic nature of 6 was established by chloride exchange by reacting Na[BPh₄] with 6 in acetonitrile to give the tetraphenylborate complex [Mo(GeCl₃)(CO)₂{Ph₂P(CH₂)PPh₂}₂][BPh₄] (7). Reaction of equimolar quantities of [MoCl(GeCl₃) (CO)₃(NCMe)₂] and PhP(CH₂CH₂PPh₂)₂ in CH₂Cl₂ at room temperature afforded the dicarbonyl complex [MoCl(GeCl₃)(CO)₂{PhP(CH₂CH₂PPh₂)₂}] (8) in good yield.     

The Coordination Chemistry of the Ylide Adduct O2CC(PPh3)2; Preparation,Crystal Structures,and Spectroscopic Properties of [Cl3In{O2CC(PPh3)2}], [Cl2Sn{O2CC(PPh3)2}], and [I2In{O2CC(PPh3)2}2]I

The betain like carbodiphosphorane CO₂ adduct O₂CC(PPh₃)₂ ( 1a ) can serve as a ligand versus hard Lewis acids from main group compounds. Thus, reaction of 1a with InCl₃, InI₃ and SnCl₂ in polar solvents leads to the addition compounds [Cl₃In{O₂CC(PPh₃)₂}] ( 2 ), [Cl₂SnO₂CC(PPh₃)₂}] ( 3 ) and the salt like compound [I₂In{O₂CC(PPh₃)₂}₂]I ( 4 ) in good yields. Whereas in the indium compounds 1a acts as a chelating ligand, in the tin compound the molecule coordinates with one oxygen atom only as a monodentate ligand. 4 has a pyramidal structure with a stereochemical active pair of electrons. All compounds could be characterized by X‐ray analyses and the usual spectroscopic methods.     

Reaction of S2CC(PPh3)2 with Silver Salts Containing Weakly Coordinating Anions; Preparation and Crystal Structures of [Ag6{S2CC(PPh3)2}4][BF4]6 · 9.75CH2CL2 and [Ag4{S2CC(PPh3)2}4][Al{OC(CF3)3}4]4 · 4.25C2H4Cl2

The betain‐like carbodiphosphorane CS₂ adduct S₂CC(PPh₃)₂ ( 1 ) reacts with Ag(I) salts which contain weakly coordinating anions such as [BF₄]^? or [Al{OC(CF₃)₃}₄]^? to produce the cluster compounds [Ag₆{S₂CC(PPh₃)₂}₄][BF₄]₆ ( 2 ) and [Ag₄{S₂CC(PPh₃)₂}₄][Al{OC(CF₃)₃}₄]₄ ( 3 ), respectively, as orange yellow crystals containing solvent molecules. In the solid state the Ag₄ unit in 3 forms a tetrahedron, and in the Ag₆ core of 2 two of the opposite edges of the tetrahedron are bridged by Ag⁺ ions. The clusters are held together by argentophilic interactions, and each sulfur atom of 1 is coordinated to four (as in 2 ) or three (as in 3 ) silver atoms. The compounds are characterized by IR and ³¹P NMR spectroscopic studies and by X‐ray diffraction analyses.     

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.     

Construction de complexes tétranucléaires de ruthénium à ossature planaire par condensation de deux unités diruthénium à l'aide de ligands pontants: Synthèse et structure moléculaire de [Ru4(CO)8{μ2-P(Cy)2}4] et de [Ru4(CO)8{μ4-P(Cy)}2{μ2-P(Cy)2}2] (Cy = cyclohexyl)

Assembly of Tetranuclear Ruthenium Complexes with Planar Metal Core by Condensation of Two Diruthenium Units Using Bridging Ligands: Synthesis and Molecular Structure of [Ru₄(CO)₈{μ₂-P(Cy)₂}₄] and [Ru₄(CO)₈{μ₄-P(Cy)}₂{μ₂}₂](Cy = Cyclohexyl) The dinuclear complexes [Ru₂(CO)₆{μ-P(Cy)₂}₂] ( 1 ) or [Ru₂(CO)₄{μ-(HCO₂)}₂{P(Cy)₂H}₂] ( 2 ) react in THF solution at 160° to give the tetranuclear complexes [Ru₄(CO)₈{μ₂-P(Cy)₂}₄] ( 3 ) and [Ru₄(CO)₈{μ₄-P(Cy)}₂{μ₂-P(Cy)₂}₂] ( 4 ), as well as the trinuclear complex [Ru₃(CO)₇(μ₂-H){μ₂-P(Cy)₂}₃] ( 5 ). If the reaction is performed at 200°, the bicapped tetranuclear species 4 is obtained in a higher yield, whereas 3 and 5 are formed in trace amounts only. The phenyl derivatives [Ru₂(CO)₆{μ-P(Ph)₂}₂] ( 6 ) or [Ru₂(CO)₄{μ-(EtCO₂)}₂{P(Ph)₂H}₂] ( 7 ) react in a similar manner to give only the complex [Ru₄(CO)₈{μ₄-P(Ph)}₂{μ₂-P(Ph)₂}₂] ( 8 ), analogous to 4 . The molecular structure of 3 consists of a planar framework of four Ru-atoms, each Ru—Ru bond being bridged by a μ₂-dicyclohexylphosphino ligand. The complex 4 represents a planar rectangular Ru core, both faces being capped by μ₄-cyclohexylphosphinidene ligands and two opposite edges being bridged by μ₂-dicyclohexylphosphino ligands.     

Chemie polyfunktioneller Liganden. 66. Reaktionen des 4-Methyl-1,2,6-triarsa-tricyclo[2.2.1.02.6]-heptan mit VIIIb-Metall-Derivaten

Acyl and Alkylidenephosphines. XlX. Molecular and Crystal Structure of 2,4-Bis (dimethyl-amino) ?1,3-diphenyl-l, 3-diphosphetane 4-Methyl-1,2,6-triarsa-tricyclo[2.2.1.0^2.6]-heptan, CH₃C(CH₂As)₃, ( 1 ) reacts with Ru₃(CO)₁₂ to the presumable polymeric [Ru(CO)₄CH₃C(CH₂As)₃]_n ( 2 ), while no reaction takes place with Os₃(CO)₁₂·Os₃(CO)₁₁CH₃CN forms with 1 at ?20°C Os₆(CO)₂₁CH₂As)₃ ( 3 ). The reaction of 1 and Co₂(CO)₈ yields [Co₂(CO)₆CH₃C(CH₂As)₃]_n ( 4 ). 1 and Ir(CO)₂(p-CH₃C₆H₄NH₂)Cl reacts in THF solution to [{Ir(CO)(THF]Cl}₃{CH₃C(CH₂As)₃}₂] ( 5 ), which contains a μ₃-(η²Cη¹O) carbonmonoxide. Upon treatment of [(μ-Cl)Ir(C₈H₁₂)]₂ with 1 [{Ir(C₈H₁₂)Cl}₉{CH₃C(CH₂As)₃}₇] ( 6 ) is obtained. The reaction of 1 with Ir(CO)(PPh₃)₂Cl yields in THF [Ir(CO)(PPh₃)(Cl)CH₃C(CH₂As)₃]₂ · THF ( 7a ). Heating of 7a in CH₂Cl₂ leads to the formation of [Ir(CO)(PPh₃)(Cl)CH₃C(CH₂As)₃ · CH₂Cl₂]₂ ( 7b ). Pt(PPh₃)₃ reacts with 1 in THF to give [Pt(PPh₃)CH₃C(CH₂As)₃]₂ · THF ( 8 ). The novel compounds are mostly insoluble or slightly soluble. They are characterized by elemental and thermogravimetric analysis, IR and, as far as possible, Raman and NMR Spectra. The results indicate that 1 react with the d⁸, d⁹, and d¹⁰ systems of the VIIIb metals under oxidative additions.     

Concerning the Reaction of the Betain‐Like Compound O2CC(PPh3)2 with Tungsten‐Carbonyl Derivatives; Preparation and Crystal Structures of [(CO)5W{η1‐O2C2(PPh3)2}] and [(CO)4W{η2‐O2C2(PPh3)2}]

The carbodiphosphorane CO₂ adduct O₂CC(PPh₃)₂ ( 1a ) reacts with [(CO)₅W(THF)] and [(CO)₃W(NCEt)₃] to produce the complexes [(CO)₅W{η¹‐O₂CC(PPh₃)₂}] ( 2 ) and [(CO)₄W{η²‐O₂CC(PPh₃)₂}] ( 3 ), respectively. Whereas in 2 the betain‐like ligand is coordinated at the tungsten atom in a monodentate manner, in 3 it acts as a chelating ligand with formation of a WO₂C four‐membered ring. As a by‐product during the reaction with the acetonitrile adduct also some crystals of the hydrolysis product [HC(PPh₃)₂]₂[W₆O₁₉] · 3C₂H₄Cl₂ (4 · 3C₂H₄Cl₂) were isolated. All compounds could be characterized by X‐ray analyses and the usual spectroscopic methods.     

Synthesis and Properties of Complexes with Unusual {MnIII4} and {MnII4} Cages

Two types of manganese complexes with [Mn₄] cores featuring the unusual distorted cube topology are presented, the first of which comprises new modifications of the reported complex [Mn^III₄(sao)₄(saoH)₄]·3CHCl₃: [Mn₄(sao)₄(saoH)₄]·1.32(C₄H₁₀O)·0.43(CH₄O) ( 1a ) and [Mn(sao)₄(saoH)₄]·0.5(CH₄O)·0.5(C₂H₃N) ( 1b ) sao = salicylaldoxime. The second, 0.55[Mn₄Cl₄(C₁₂H₉N₂O)₄(CH₃OH)₂(H₂O)₂]·0.45[Mn₄Cl₄(C₁₂H₉N₂O)₄(CH₃OH)₄] ( 2 ), is the first reported case of a {Mn^II₄} core of this topology besides known {Mn^III₄} compounds. Differences between the {Mn^II₄} and {Mn^III₄} situation are discussed, and so far overlooked differences in magnetic properties between different {Mn^III₄} compounds are pointed out.     

Thiochlorowolframate von Wolfram(V) und -(VI). Die Kristallstrukturen von PPh4[WSCl4] und (PPh4)2[WS2Cl4] · 2 CH2Cl2

Thiochlorowolframates with Tungsten(V) and (VI). Crystal Structures of PPh₄[WSCl₄] and (PPh₄)₂[WS₂Cl₄] · 2 CH₂Cl₂ Diamagnetic (NEt₄)₂[WSCl₄]₂, having tungsten atoms linked via sulfur atoms, is obtained by the reaction of WCl₅ with NEt₄SH as well as by the reduction of WSCl₄ with NEt₄I in dichloromethane. If the reduction is performed with PPh₄I, PPh₄[WSCl₄] with monomer anions is formed. Reaction of WCl₆ with H₂S in dichloromethane yields brown, insoluble WS₂Cl₂ which has terminal W?S groups and bridging W? S? W groups according to its IR spectrum. WS₂Cl₂ and PPh₄Cl react to afford PPh₄[WS₂Cl₃] · 2 CH₂Cl₂ and (PPh₄)₂[WS₂Cl₄] · 2 CH₂Cl₂. IR spectra are reported. The crystal structures of PPh₄[WSCl₄] and (PPh₄)₂[WS₂Cl₄] · 2 CH₂Cl₂ were determined by X-ray diffraction. PPh₄[WSCl₄]: tetragonal, space group P4/n, Z = 2, a = 1292.3 pm, c = 763.2 pm; R = 0.054 for 898 observed reflexions. The [WSCl₄]^? ion has the structure of a square pyramid with a rather short W?S bond of 206 pm length. (PPh₄)₂[WS₂Cl₄] · 2 CH₂Cl₂: triclinic, space group P1 , a = 1017.7, b = 1114.5, c = 1243.4 pm, α = 70.61, β = 79.73, γ = 80.80°; R = 0.076 for 1804 reflexions. The [WS₂Cl₄]^2? has cis configuration; as it is situated on an inversion center it shows positional disorder.     

Synthesis and structures of new heteronuclear cluster complexes [PPh4][Fe4Rh3Se2(CO)16] and [PPh4]2[Fe3Rh4Te2(CO)15]

The reaction of the K₂[Fe₃Q(CO)₉] clusters (Q = Se or Te) with Rh₂(CO)₄Cl₂ under mild conditions is accompanied by complicated fragmentation of cores of the starting clusters to form large heteronuclear cluster anions. The [PPh₄][Fe₄Rh₃Se₂(CO)₁₆] and [PPh₄]₂[Fe₃Rh₄Te₂(CO)₁₅] compounds were isolated by treatment of the reaction products with tetraphenylphosphonium bromide. The structures of the products were established by X-ray diffraction. In both compounds, the core of the heteronuclear cluster consists of two octahedra fused via a common Rh₃ face. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 775–778, May, 2006.     

Platinum,iridium and rhodium complexes with substituted bis-(diphenylphosphino)methane ligands Ph2PCH(R)PPh2 (R = Me,Ph or SiMe3)

Substituted phosphines of the type Ph₂PCH(R)PPh₂ and their Pt^II complexes [PtX₂{Ph₂PCH(R)PPh₂}] (R = Me, Ph or SiMe₃; X = halide) were prepared. Treatment of [PtCl₂(NCBu^t)₂] with Ph₂PCH(SiMe₃)-PPh₂ gave [PtCl₂(Ph₂PCH₂PPh₂)], while treatment with Ph₂PCH(Ph)PPh₂ gave [Pt{Ph₂PCH(Ph)PPh₂}₂]Cl₂. Reaction of p-MeC₆H₄C≡CLi or PhC≡CLi with [PtX₂{Ph₂PCH(Me)PPh₂}] gave [Pt(C≡CC₆H₄Me-p)₂-{Ph₂PCH(Me)PPh₂}] (X = I) and [Pt{Ph₂PC(Me)PPh₂}₂](X = Cl),while reaction of p-MeC₆H₄C≡CLi with [Pt{Ph₂PCH(Ph)PPh₂}₂]Cl₂ gave [Pt{Ph₂PC(Ph)PPh₂}₂]. The platinum complexes [PtMe₂(dpmMe)] or [Pt(CH₂)₄(dpmMe)] fail to undergo ring-opening on treatment with one equivalent of dpmMe [dpmMe = Ph₂PCH(Me)PPh₂]. Treatment of [Ir(CO)Cl(PPh₃)₂] with two equivalents of dpmMe gave [Ir(CO)(dpmMe)₂]Cl. The PF₆ salt was also prepared. Treatment of [Ir(CO)(dpmMe)₂]Cl with [Cu(C≡CPh)₂], [AgCl(PPh₃)] or [AuCl(PPh₃)] failed to give heterobimetallic complexes. Attempts to prepare the dinuclear rhodium complex [Rh₂(CO)₃(μ-Cl)(dpmMe)₂]BPh₄ using a procedure similar to that employed for an analogous dpm (dpm = Ph₂PCH₂PPh₂) complex were unsuccessful. Instead, the mononuclear complex [Rh(CO)(dpmMe)₂]BPh₄ was obtained. The corresponding chloride and PF₆ salts were also prepared. Attempts to prepare [Rh(CO)(dpmMe)₂]Cl in CHCl₃ gave [RhHCl(dpmMe)₂]Cl. Recrystallization of [Rh(CO)(dpmMe)₂]BPh₄ from CHCl₃/EtOH gave [RhO₂(dpmMe)₂]BPh₄. Treatment of [Rh(CO)₂Cl₂]₂ with one equivalent of dpmMe per Rh atom gave two compounds, [Rh(CO)(dpmMe)₂]Cl and a dinuclear complex that undergoes exchange at room temperature between two formulae: [Rh₂(CO)₂(μ-Cl)(μ-CO)(dpmMe)₂]Cl and [Rh₂(CO)₂-(μ-Cl)(dpmMe)₂]Cl. This revised version was published online in June 2006 with corrections to the Cover Date.     

Reaktionen des [η2-{P–PtBu2}Pt(PPh3)2] und [η2-{P–PtBu2}Pt(dppe)] mit Metallcarbonylen. Bildung von [η2-{(CO)5M · PPtBu2}Pt(PPh3)2] (M = Cr,W) und [η2-{(CO)5Cr · PPtBu2}Pt(dppe)]

Coordination Chemistry of P-rich Phosphanes and Silylphosphanes. XVI [1] Reactions of [g²-{P–P^tBu₂}Pt(PPh₃)₂] and [g²-{P–P^tBu₂}Pt(dppe)] with Metal Carbonyls. Formation of [g²-{(CO)₅M · PP^tBu₂}Pt(PPh₃)₂] (M = Cr, W) and [g²-{(CO)₅Cr · PP^tBu₂}Pt(dppe)] [η²-{P–P^tBu₂}Pt(PPh₃)₂] 4 reacts with M(CO)₅ · THF (M = Cr, W) by adding the M(CO)₅ group to the phosphinophosphinidene ligand yielding [η²-{(CO)₅Cr · PP^tBu₂}Pt(PPh₃)₂] 1 , or [η²-{(CO)₅W · PP^tBu₂}Pt(PPh₃)₂] 2 , respectively. Similarly, [η²-{P–P^tBu₂}Pt(dppe)] 5 yields [η²-{(CO)₅Cr · PP^tBu₂}Pt(dppe)] 3 . Compounds 1 , 2 and 3 are characterized by their ¹H- and ³¹P-NMR spectra, for 2 and 3 also crystal structure determinations were performed. 2 crystallizes in the monoclinic space group P2₁/n (no. 14) with a = 1422.7(1) pm, b = 1509.3(1) pm, c = 2262.4(2) pm, β = 103.669(9)°. 3 crystallizes in the triclinic space group P1 (no. 2) with a = 1064.55(9) pm, b = 1149.9(1) pm, c = 1693.2(1) pm, α = 88.020(8)°, β = 72.524(7)°, γ = 85.850(8)°.     

Synthesis, Chemical Characterization, and Molecular Structure of Au8{Fe(CO)4}4(dppe)2 and Au6Cu2{Fe(CO)4}4(dppe)2

The new Au₈{Fe(CO)₄}₄(P^P)₂ and Au₆Cu₂{Fe(CO)₄}₄(P^P)₂ (P^P=dppm, dppe) neutral cluster compounds were isolated in good yields by condensation of the [Au₃{Fe(CO)₄}₂(P^P)]^- anions with Au(SEt₂)Cl and CuCl, respectively, and have been characterized by IR, NMR and microanalyses. The molecular structures of Au₈{Fe(CO)₄}₄(dppe)₂ and Au₆Cu₂{Fe(CO)₄}₄(dppe)₂ have been determined by X-ray diffraction studies. Both molecules adopt a stereogeometry of the heavy atoms consisting of a triangulated and corrugated ribbon twisted around the elongation direction. Contrary to the expectations the latter displays the two copper atoms in the sites of highest connectivity. This implies that site exchange between copper and gold occurs during the synthesis.     

[SnI8{Fe(CO)4}4]2+: Highly Coordinated Sn+III8 Subunit with Fragile Carbonyl Clips

[SnI₈{Fe(CO)₄}₄][Al₂Cl₇]₂ contains the [SnI₈{Fe(CO)₄}₄]²⁺ cation with an unprecedented highly coordinated, bicapped SnI₈ prism. Given the eightfold coordination with the most voluminous stable halide, it is all the more surprising that this SnI₈ arrangement is surrounded only by fragile Fe(CO)₄ groups in a clip‐like fashion. Inspite of a predominantly ionic bonding situation in [SnI₈{Fe(CO)₄}₄]²⁺, the I^????I^? distances are considerably shortened (down to 371 pm) and significantly less than the van der Waals distance (420 pm). The title compound is characterized by single‐crystal structure analysis, spectroscopic methods (EDXS, FTIR, Raman, UV/Vis, Mössbauer), thermogravimetry, and density functional theory methods.     

Synthese und Kristallstruktur von (PPh4)2[Mo2(S2)2Cl8] · 2 CH3CN und seine topotaktische Umwandlung zu (PPh4)2[Mo2(S2)2Cl8]

Synthesis and Crystal Structure of (PPh₄)₂[Mo₂(S₂)₂Cl₈] · 2 CH₃CN and its Topotactic Transformation to (PPh₄)₂[Mo₂(S₂)₂Cl₈] MoS₂Cl₃ was prepared from molybdenum and S₂Cl₂ at 200 °C. Its reaction with PPh₄Cl in acetonitrile yielded (PPh₄)₂[Mo₂(S₂)₂Cl₈] · 2 CH₃CN. In vacuum or upon warming, it loses the acetronitrile without degradation of the crystals. According to the X-ray crystal structure determinations both compounds, with and without acetonitrile, are triclinic. They contain the same [Cl₄Mo(μ-S₂)₂MoCl₄]^2– ions, in which the Mo atoms are joined by two disulfido groups and an Mo–Mo bond. Details of the crystal packings and their topotactic transformation are given.