REACTIONS OF CARBONYLSULPHIDE WITH [Rh(PPh3)3CI] AND [Pt(PPh3)3]

Abstract

Activation of small inorganic molecules (H₂, N₂, O₂, CO, NO, CO₂, SO₂, CS₂) by the complexes of transition metal ions like Rh(I), Ir(I), Pt(O) and Ru(II) have gained considerable interest during the last decade.^1–8 Because of the similarity of CO₂ and CS₂ molecules with COS, one would expect COS to form complexes with the transition metal ions analogous to those of CO₂ and CS₂. In addition, COS being susceptible to decomposition into CO and S, could also form carbonyl complexes. Until now, the only reaction of COS that has been successfully carried out is with [Pt(PPh₃)₃] which resulted in the formation of [Pt(COS)(PPh₃)₂] and [Pt₂S(CO) (PPh₃)₃]. ^8,9 It will, therefore, be interesting to study further the reactions of COS with the complexes of transition metal ions. The results of a preliminary study of such reactions with [Rh(PPh₃)₃Cl] and [Pt(PPh₃)₃] are reported in this communication.     

(PPh4)2[OsCl3(NO)(SnCl3)2] Synthese,IR-Spektrum und Kristallstruktur

(PPh₄)₂[OsCl₃(NO) (SnCl₃)₂]; Preparation, I.R. Spectrum, and Crystal Structure (P(C₆H₅)₄)₂[OsCl₃(NO)(SnCl₃)₂] yields from the reaction of OsCl₃(NO) with PPh₄-[SnCl₃] in dichloro methane forming red crystals. The complex crystallizes monoclinic in the space group C2/c with four formula units per unit cell. The crystal structure was determined by aid of X-ray diffraction data (2261 independent, observed reflexions, R = 4.9%). The cell parameters are a = 1369, b = 1989, c = 2088 pm, β = 99.54°. The structure consists of tetraphenyl phosphonium cations and [OsCl₃(NO)(SnCl₃)₂]^2?-anions. In the anion the osmium is coordinated octahedrally by three chlorine atoms (mean bond length r Os? Cl 238 pm), two SnCl₃ groups in transposition to each other (r Os? Sn 265 pm) and the N-atom of the covalently bonded nitrosyl ligand (r Os? N 173 pm). The i.r. spectrum of the anion is reported and assigned.     

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.     

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.     

The Binary Group 4 Azides [PPh4]2[Zr(N3)6] and [PPh4]2[Hf(N3)6]

The binary zirconium and hafnium polyazides [PPh₄]₂[M(N₃)₆] (M=Zr, Hf) were obtained in near quantitative yields from the corresponding metal fluorides MF₄ by fluoride–azide exchange reactions with Me₃SiN₃ in the presence of two equivalents of [PPh₄][N₃]. The novel polyazido compounds were characterized by their vibrational spectra and their X‐ray crystal structures. Both anion structures provide experimental evidence for near‐linear M‐N‐N coordination of metal azides. The species [M(N₃)₄], [M(N₃)₅]^? and [M(N₃)₆]^2? (M=Ti, Zr, Hf) were studied by quantum chemical calculations at the electronic structure density functional theory and MP2 levels.     

Reaction of tetrakis (trifluoromethyl)allene with anions [CpMo(CO)2PPh3]- and [CpW(CO)2PPh3]

Conclusions The-dienyl complexes are formed when tetrakis (trifluoromethyl)allene is reacted with dicarbonyltriphenylphosphine--cyclopentadienylmolybdate and dicarbonyltriphenylphosphine--cyclopentadienyltungstate.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 681–683, March, 1978.     

Codimerization of quadricyclane withendo,exo-hexacyclo[9.2.1.02,10.03,8.04,6.05,9]tetradec-12-ene catalyzed by the Pd(PPh3)4 complex

endo,exo-Hexacyclo[9.2.0^2,10.0^3,8.0^4,6.0^5,9]tetradec-12-ene (1) undergoes cyclocodimerization with quadricyclane (Q) in the presence of the Pd(PPh₃)₄ complex to giveexo,exo,endo,exo-decacyclo[9.9.1.0^2,10.0^3,8.0^4,6.0^5,9.0^12,20.0^13,18.0^14,16.0^15,19]heneicosane (2) andendo,exo,endo,exo-decacyclo[9.9.1.0^2,10.0^3,8.0^4,6.0^5,9.0^12,20.0^13,18.0^14,16.0^15,19]heneicosane (3) in a ratio of 10 7 (yield up to 26 %). Simultaneously, homocyclotrimerization of Q occurs to give three known C₂₁ hydrocarbons (4–6). The yields of compounds2 and3 and the selectivity of the process depend considerably on the reaction conditions and the molar ratio of1 and Q. Compounds2 and3 that were obtained were characterized by¹³C NMR spectra.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1983–1985, November, 1994.     

Synthesen und Kristallstrukturen von [Pd9As8(PPh3)8] und [Pd9Sb6(PPh3)8]

Syntheses and Crystal Structures of [Pd₉As₈(PPh₂)₈] and [Pd₉Sb₆(PPh₃)₈] [PdCl₂(PPh₃)₂] reacts with As(SiMe₃)₃ to give the new cluster [Pd₉As₈(PPh₃)₈] ( 4 ). 4 has been characterized by X-ray crystal structure analysis. It is a molecule in which four [Pd₂(PPh₃)₂]-units are bridged by As₂-units. A further Pd atom is located in the centre of the cluster. 4 crystallizes in the space group C2/c with four formula units per unit cell. The lattice constants at 200 K are: a = 3 970.6(3), b = 1 648.90(16), c = 3 266.30(20) pm, β = 131,44(4)°. The reaction of [PdCl₂(PPh₃)₂] with Sb(SiMe₃)₃ yields [Pd₉Sb₆(PPh₃)₈] ( 5 ). 5 consists of a body centred cubic Pd₉-cluster. All of the cube faces are capped by μ₄-Sb-ligands. 5 crystallizes in the space group Pn3 with two formula units per unit cell. The lattice constants at 200 K are: a = b = c = 1 995.4(2) pm.     

Variable-Temperature and -Pressure 31P-NMR Study of the Intramolecular PPh3 Migration in the Cluster Compound [Ir2Rh2(CO)11PPh3]

The reaction of [Ir₂Rh₂(CO)₁₂] with 1 mol-equiv. of PPh₃ yields [Ir₂Rh₂(CO)₁₁PPh₃] ( 1 ) as a mixture of two isomers with the phosphine ligand axially bound either to one basal Rh-atom in the kinetically preferred isomer 1 R or to one basal Ir-atom in the thermodynamically preferred isomer 11 . Both isomers are fluxional on the ¹³C-NMR time scale at low temperature due to CO scrambling. Around room temperature, a new type of fluxional process starts to operate which is responsible for the isomerisation 1R?11 , i.e. the intramolecular migration of the reputedly inert PPh₃ ligand from one metal centre to another. The activation volumes of conversions 1R → 11 and 11 → 1R are both positive, indicating that the migration of PPh₃ is dissociative in character. This article reports the first application of variable pressure ³¹P-NMR to mechanistic studies.