Reinhard Kramolowsky

Synthese und koordinationsverhalten ambidenter chelatliganden : II. Darstellung und charakterisierung von carbonylmangan(I)-komplexen mit organosubstituierten phosphino-dithioformiaten oder -thioformamiden als weitere liganden☆

Abstract [MnBr(CO) 5 ] reacts with the potassium diorganylphosphino-dithioformates or -thioformamides KS(X)CPR 2 (X = S, NPh: R = Ph, Cy; Cy = cyclo-C 6 H 11 ), respectively, to give the monomeric tetracarbonylmanganese(I) complexes [Mn{S(X)CPR 2 }(CO) 4 ] (IaId), whereas with the thioureas R′ 2 NC(S)NPhH (R′ = Me, Et) dinuclear carbonylthioureidomanganese(I) complexes of the type [{Mn[μ-S(NPh)CNR′ 2 ](CO) 3 } 2 ] are obtained, in which the thio-anions act as bridging ligands. In the reactions of the phosphinothioformamides R 2 PC(S)NPhH (R = Ph, Cy) with [MnBr(CO) 5 ] the monomeric bromotricarbonyl(phosphinothioformamid)manganese(I) complexes fac -[MnBr(CO) 3 {R 2 PC(S)NPhH}] (IIIa, IIIb) are formed together with [Mn{S(NPh)CPPh 2 }(CO) 4 ] (Ic) (for R = Ph) or cis -[MnBr(CO) 4 (PCy 2 H)] (for R  Cy). The IR, Raman and 31 P NMR spectra of the complexes are discussed, in particular in their relation to the bonding mode of the thio-ligands. In accordance with data the thio-anions and neutral phosphinothioformamides in Ia–Id and IIIa, IIIb form four-membered chelate rings bonded via phosphorus and sulfur. For the complexes IIIa, IIIb the spectroscopic results have been verified by an X-ray crystal structure determination of IIIa.

55Mn NMR characteristics of carbonylmanganese complexes with hetero-substituted dithioformato-, thioformamido- and thioformamide ligands [1]

Abstract Complexes wth the general formulae [(CO)4MnS2CZ] (Z = OR, SR, NR2, PR2, P(S)R2, AsPh2, Ph), [(CO)4 MnSC(NR′)P R2], [(CO)4 MnSC(NR′)P(S) R2] and fac-[(CO)3Br MnSC(NHR′)P R2] exhibit 55Mn chemical shift ranges which allow classification with respect to the mode of coordination of the thio ligand and the ring size of the chelate structure. Shielding decreases, in the series chelate-4 ring (S,P-coordinated) > chelate-5 ring (S,S′) > chelate-4 ring (S,S′). Within the group of [(CO)4MnS2CZ] complexes, shielding decreases in the order NR2 > OR > Ph > AsPh2 > P(S)R2 > SR. The trends are explained in terms of varying contributions of molecular parameters to the paramagnetic term of the shielding constant, and related to structure data. There is no apparent correlation between line widths of the 55Mn resonance signals and molecular parameters.

Synthese und koordinationsverhalten ambidenter chelatliganden : III. Kristall-und molekülstrukturen der carbonyl-mangan(I)-komplexe fac-[MnBr(CO)3 {Ph2PC(S)NPhH}] und [Mn{S(NPh)CPPh2}(CO)4]. Neutrale phosphinothioformamide und deren deprotonierte, anionische derivate als S,P-chelatliganden

Abstract The crystal and molecular structures of the complexes [Mn{S(NPh)CPPh 2 }-(CO) 4 ] (Ic) and fac -[MnBr(CO) 3 {Ph 2 PC(S)NPhH}] (IIa) have been determined by X-ray diffraction analyses. Ic crystallizes in the triclinic space group P 1 with a 989.3(6), b 1049.7(5), c 1093.0(7) pm, α 91.42(3), β 97.02(4), γ 100.64(4)° and Z  2. Crystals of IIa are monoclinic, space group C2/c with a 2446.0(8), b 1316.0(3), c 1945.0(6) pm, β 132.68(2)° and Z  8. Based on 3264 (Ic) and 2570 (IIa) reflections the structures have been solved by conventional methods and refined by least-squares methods to R ( R w ) values of 0.055 (0.045) (Ic) and 0.059 (0.064) (IIa), respectively. The phosphinothioformamide anion Ph 2 PC(NPH)S - in Ic as well as the protonated neutral phosphinothioformamide Ph 2 PC(S)NPhH in IIa coordinate via phosphorus and sulfur forming four-membered, slightly folded chelate rings. On the basis of the CN, CP and CS distances the bonding features of the S,P -coordinated phosphino-thioformamide anion and -thioformamide are compared and discussed. The MnP bond length in Ic and IIa is 231.6(1) pm. On the other hand the MNS distances with 239.8(1) in Ic and 238.1(3) pm in IIa are significantly different.

SYNTHESIS AND CRYSTAL STRUCTURE OF CD(C-C6H11)2P(SE)C(S)NPH2

The synthesis and spectroscopic characterisation of [Cd(c-C 6 H 11 ) 2 P(Se)C(S)NPh 2 ] is reported. The [(c-C 6 H 11 ) 2 P(Se)C(S)NPh] anions are chelating and define a tetrahedral Se 2 S 2 donor set about the cadmium atom. The tetrahedral CdSe 2 S 2 arrangement has been characterised for the first time crystallographically and in the present case the Cd Se bond distances lie in the range 2.613(1)–2.625(1)Aand Cd S 2.488(3)–2.523(3)A. Crystals are triclinic, space group Pl¯ with unit cell dimensions a = 19.848(4), b = 20.485(3). c = 10.969(2)A, α = 105.49(1), β = 102.37(1), γ = 101.06(1)°, Z = 4. The structure was refined to final R = 0.051 for 7071 reflections.

Binuclear diorganophosphinothioformamido complexes of gold(I): Synthesis and crystal structure of [Au(Ph2PC(S)NPh)]2 and related systems

Abstract Binuclear gold compounds, [Au(R2PC(S)NR′)]2, were characterized from the reactions of HAuCl4 or Ph3PAuCl with R2PC(S)N(H)R′. The complexes feature bidentate bridging ligands that link two gold centres leading to eight-membered metallacycles and linear SAuP coordination geometries. In the case of [Au(Ph2PC(S)NPh)]2, crystal structure analysis shows the presence of two conformations in the one lattice, i.e. an extended chair and a twisted conformation.

Darstellung und eigenschaften von O-alkylxanthogenato-carbonyl-komplexen des mangans(I) und rhenium(I)

Zusammenfassung The O-alkylxanthatocarbonyl complexes [M(S2COR)(CO)4] (M = Mn, Re; R = Me, Et) and [Mn(S2COR)(CO)3 (PR′3)] (R′ = Et, Ph) have been prepared and their geometric and electronic structures discussed with reference to the IR, 1H NMR and mass spectra.

Electron spin resonance spectra of dinitrosyltriorganoantimony-ironbromides in solution

ESR data of the complexes Fe(NO)2SbR3Br (R = C2H5, C6H5, and 4—(H3C)2NC6H4) in solution are presented. The observed hyperfine coupling due to bromine and antimony is interpreted including second order contributions. Nuclear quadrupole effects are discussed and found to be detectable in the antimony hyperfine pattern.

NMR-SPEKTROSKOPISCHE CHARAKTERISIERUNG UND RÖNTGENSTRUKTURANALYSE VON TRIBENZYLPHOSPHANSELENID

Abstract Tribenzylphosphine selenide (Bz3PSe) has been synthesized by reacting Bz3P with KSeCN in CH3CN. Bz3PSe crystallizes (from CHCl3 solution) in the trigonal space group R3 with a = 16,037(4) and c = 6,168(2) A and three discrete molecules in the unit cell. The absolute configuration of these chiral molecules having ideal C3 symmetry has been determined. The title compound has been further characterised by 1H, 13C, 31P and 77Se NMR spectroscopy. Tribenzylphosphanselenid (Bz3PSe), das durch Umsetzung von Bz3P mit KSeCN in CH3CN erhalten wird, kristallisiert (aus CHCl3-Losung) in der trigonalen Raumgruppe R3 mit a= 16,037(4) und c = 6.168(2) A. In der Elementarzelle liegen drei diskrete, chirale Molekule mit idealer C3-Symmetrie vor, deren absolute Konfiguration bestirnmt werden konente. Zusatzlich wird die Titelverbindung anhand ihrer 1H-, 13C-, 31P- und 77Se-NMR-Daten charakterisiert.

Koordinationschemie von Liganden mit den Donatoren Phosphor und Schwefel, I Nickel(II)-Komplexe mit Phosphinomethylthioethera als Liganden Gleichgewicht zwischen planarem und tetraedrischem Nickel(II) / Coordination Chemistry of Ligands with the Donors Phosphorus and Sulfur, I Nickel(II) Complexes with Phosphinomethylthioethers as Ligands A Planar-Tetrahedral Equilibrium with Nickel(II)

Abstract The preparation and structural characterization of phosphinomethylthioethernickel(II) complexes of the general type [NiX2(Ph2PCH2SR)2] (X = CI, Br, I, NCS: R = Me, Ph) are reported. In all the complexes the phosphinomethylthioethers act as monodentate ligands coordinating via the phosphorus atom. The isothiocyanate complexes are diamagnetic both in solution and in the solid state and have been assigned trans-planar configuration. As shown by magnetic measurements and by electronic spectroscopy, the halo complexes exhibit a square-planar (diamagnetic) ⇄ distorted-tetrahedral (paramagnetic) equilibrium in solution, while in the solid state the complexes are either square-planar or distorted-tetrahedral. For the complex [NiBr2(Ph2PCH2SMe)2] both isomers have been isolated in the solid state.

Dithiolate und Dithiolato-Komplexe, I

The complexes Bis(η-cyclopentadienyl)-1,1-dithiolatovanadium(IV) [VCp2(S2C=Y)] (Y = S,NCN,C(CN)2,C(CN) (CO2Et),C(CO2Et)2)* and Bis(η-cyclopentadienyl)-1,2-dicyanoethylene-1,2-dithiolatovanadium(IV) [VCp2(S2C2(CN)2)] are prepared by reaction of [VCp2Cl2] and the appropiate alkali metal salt K2S2C=Y or Na2S2C2(CN)2. The complexes are characterized by molecular weight, electric conductivity and magnetic measurements. The IR, electronic and ESR spectra are discussed.