Karen Meyer-Bäse

Bis(perhalogenophenyl) derivatives of palladium(II) and platinum(II) containing S2CP(C6H11)3 as a mono- or bi-dentate ligand. Crystal structures of cis-[Pd(C6F5)2{S2CP(C6H11)3}] and cis-[Pt(C6F5)2{SC(S)P(C6H11)3}(CO)]

Addition of S2CP(C6H11)3 to solutions of [M(C6X5)2(OC4H8)2](M = Pd or Pt; X = F or Cl) affords the derivatives [M(C6X5)2{S2CP(C6H11)3}], which are the first containing S2CP(C6H11)3 chelate bonded to palladium or platinum. Reaction of the above complexes with 1 mol equivalent of a neutral monodentate ligand L leads to [M(C6X5)2{SC(S)P(C6H11)3}L](L = PPh3, X = F, M = Pd or Pt; L = CO, X = F or CI, M = Pt; L = pyridine, X = F, M = Pt) where S2CP(C6H11)3 is monodentate. The structure of one example of each of these types has been determined by single-crystal X-ray crystallography: cis-[Pd(C6F5)2{S2CP(C6H11)3}], space group C2/c, a= 26.654(8), b= 11.519(3), c= 24.223(7)A, β= 116.93(3)°, Z= 8, and R= 0.045; cis-[Pt(C6F5)2{SC(S)P(C6H11)3}(CO)], space group P, a= 9.864(2), b= 14.202(3), c= 14.638(5)A, α= 93.44(3), β= 103.11(2), γ= 105.45(2)°, Z= 2, and R= 0.042. The co-ordination at the metal atoms is planar. In the palladium derivative the chelating S2CP group makes a dihedral angle of 12.3° to the ligand plane; in the platinum derivative the corresponding angle formed by the monodentate ligand is 55.3°.

Synthesis of pentafluorophenyl(ylide)silver(I) complexes: X-ray structures of two modifications of [Ag(C6F5)(CH2PPh3)]

Monomeric silver ylide complexes [Ag(C6F5)(CH2ER3)](ER3= PPh3, PPh2Me, PPhMe2, or AsPh3) can be prepared by the reaction of Ag(CF3CO2) with Li(C6F5) and [ER3Me][CF3CO2]. The free ylides CH2PPh3, CH2PPh2Me, or CH(CO2Me)PPh3 react with Ag(C6F5) or AgClO4 to afford [Ag(C6F5)(ylide)] or [Ag(CH2PPh3)2]ClO4 respectively. Several novel ylide-transfer reactions from silver ylides to other silver or gold centres are reported. The structures of two forms of [Ag(C6F5)(CH2PPh3)] have been established. The molecules differ mainly in the orientation of one phenyl ring. The C6F5 groups are highly distorted at the ipso carbon [C–C–C 113.1 (5) and 112.5(5)°].

Crown-shaped tetrametallic imidoyl complexes of palladium. X-Ray crystal structure of [{[Pd2{µ-C(C6F5)NMe}2](µ-Cl)(µ-MeCO2)}2]

The complexes [{[Pd2{µ-C(C6F5)NR1}2](µ-X1)(µ-X2)}n](R1= Me or p-tolyl; X1= X2= Cl) and their derivatives (X1= Cl, X2= MeCO2 or CF3CO2; X1= X2= MeCO2 or CF3CO2), obtained by metathetical reactions with the corresponding silver salts, are shown to be tetrametallic (n= 2) by molecularweight determinations. Their structures are discussed on the basis of 1H and 19F n.m.r. data. The crystal structure of the title complex has been solved by X-ray diffraction methods [space group P21/n, a= 14.380(4), b= 19.980(4), c= 15.976(4)A, β= 103.51(3)°, Z= 4, R′= 0.046 for 5 428 unique observed reflections]. The tetrametallic molecule is crown-shaped. The bond lengths at palladium reflect the strong trans influence of the imidoyl-C atom; the Pd–Cl bonds trans to C are amongst the longest known.

Reaction of nitrobenzene with [M3(CO)12](M = Fe or Ru) in the presence of [Co2(CO)8]: isolation and structure of [Ru3(CO)7(NPh)(η6-C6H6)]

The complexes [Ru3(CO)7(NPh)(C6H6)](1) and [FeCo2(CO)9(NPh)](2) are formed in the reactions between PhNO2 and [M3(CO)12](M = Ru or Fe) only when [Co2(CO)8] is present. The structure of (1) has been determined by X-ray diffraction; it contains triply bridging CO and PhN ligands and an η6-benzene ligand co-ordinated to only one metal atom.

Pentafluorophenyl(dithiocarbamate)gold(III) complexes: crystal and molecular structure of (C6F5)2Au{S2CN(CH2Ph)2}

Abstract Addition of dialkyldithiocarbamate ligands to solutions of Au(C 6 F 5 ) 3 (tht) gives either monomeric Q[Au(C 6 F 5 ) 3 (η 1 -S 2 CNR 2 )] (Q = N(PPh 3 ) 2 or NBu 4 ; R = Me, Et, CH 2 Ph) or binuclear dithiocarbamate-bridged complexes. NBu 4 (μ-S 2 CNR 2 ){Au(C 6 F 5 ) 3 } 2 ]. When binuclear [Au(μ-Cl)(C 6 F 5 ) 2 ] 2 is used as gold source, neutral mononuclear complexes [Au(C 6 F 5 ) 2 (η 2 -S 2 CNR 2 )] are obtained. The structure of [Au(C 6 F 5 ) 2 {η 2 -S 2 CN(CH 2 Ph) 2 }] has been determined by X-ray diffraction.

Synthesis and reactivity of neutral complexes of the types [AuX3(ylide)l and trans-[Au(C6F5)X2(ylide)] (X = halide or pseudohalide). X-ray structure of [Au(SCN)3(CH2PPh3)]

Abstract Halogens (Cl 2 or Br 2 ) add oxidatively to ylide-gold(I) complexes [AuX- (CHRPR′ 3 )] or [Au(C 6 F 5 )(CH 2 PR 3 )] to give stable gold(III) derivatives of the types [AuX 3 (CHRPR′ 3 )] (X = Cl, Br) or trans -[Au(C 6 F 5 )X 2 (CH 2 PR 3 ],which can be converted into other halo or pseudohalo comple trans -[Au(C 6 F 5 )(SCN) 2 (CH 2 PPh 2 Me)]. The structures have been assigned on the basis of spectral (IR and NMR) and X-ray data.

Untersuchungen am System Triphenylphosphingold(I)/Sulfat: Synthese und Röntgenstrukturanalyse von (Ph3PAu)2SO4 · CH3OH/ Studies of the System Triphenylphosphinegold(I)/Sulphate: Synthesis and Crystal Structure of (Ph3PAu)2SO4 · CH3OH

Abstract The reaction between (triphenylphosphine)acetatogold(I) and concentrated sulphuric acid in methanol leads to (Ph3PAu)2SO4 (1) or [(Ph3PAu)3O]+ HSO4- , depending on the acid concentration. The crystal structure of the methanol solvate of (1) was determined [C2/c, a = 1348.3(2), b = 1451.0(2), c = 1853.8(3) pm, β = 99.90(2)°, Z = 4, R = 0.037 for 3138 unique observed reflections], 1 possesses crystallographic twofold symmetry, with Au -O 206.3, Au -P 221.6 pm. The corresponding selenate is isomorphous.

Darstellung und Struktur des N-Thiobis-N′ -(phenylsulfonyl)schwefeldiimids / Synthesis and Structure of N-Thiobis-N′-(phenylsulfonyl)sulfurdiimide

The reaction of S4N4 with PhSO2NCl2 proceeds with formation of (PhSO2NSN)2S 2. The main product 2 was characterized by an X-ray structure determination. [P21/c, a = 996.8(2), b = 1733.0(2), c = 1131.2(1) pm, β = 114.69(1)°, Z = 4, R = 0.044 for 1911 reflections.] 2 contains a sulfur-nitrogen chain with a planar central N4S3-Unit. The substituents at the NSN-groups are in cis-trans positions. 2 reacts with AgAsF6 to yield the 1:1 complex 3; attempts to recrystallise this from CH2Cl2 led to 2 · CH2Cl2, which was also subjected to a crystal structure determination [P1̄, a = 554.4(2), b = 1313.5(4), c = 1541.3(4) pm, α = 111.05(2), β = 94.61(2), γ = 92.24(2)°. Z = 2. R = 0.088 for 1728 reflections]. Minor differences between the two forms of 2 are observed.