Winfried Hellmann

Darstellung und Röntgenstrukturanalyse von 26 Thiomolybdato- bzw. Thiowolframato-und eines Selenowolframato-Komplexes

SummaryThe preparation and characterization by X-ray structure analysis of the following chalcogenometalato complexes are reported: 1: [(Ph3P)2N]2(NEt4)[Fe(WS4)2]·2MeCN; 2: [(Ph3P)2N]2(NEt4)[Cu(WS4)2]·2MeCN; 3: [(Ph3P)2N]2(NEt4)[Ag(MoS4)2]·MeCN; 4: [(Ph3P)2N]2(NEt4)[Ag(WS4)2]·MeCN; 5: (PPh4)2[Hg(WS4)2]; 6: (PPh4)2[Au2(WOS3)2]; 7: (PPh4)4[Pb2(MoS4)4]; 8: (PPh4)4[Pb2(WS4)4]; 9: (NEt4)2[Fe(WS4)2(H2O)2]; 10: [Fe(DMSO)6][Cl2Fe(MoS4)]; 11: [Fe(DMSO)6][Cl2Fe(MoOS3)]; 12: (PPh4)(NMe3CH2Ph)[Cl2Fe(WS4)]; 13: [Fe(DMF)6][Cl2Fe(WS4)]; 14: (PPh4)2[Cl2Fe(WS4)]; 15: (PPh4)2[Cl2Fe(WS4)]·2 CH2Cl2; 16: (PPh4)2[NCCu(MoS4)]; 17: (PPh4)2[NCAg(MoS4)]; 18: (PPh4)2[NCAg(WS4)]; 19: (PPh4)2[Cu3Cl3(MoOS3)]; 20: (PPh4)2[Cu3Br3(MoS4)]·MeCN; 21: (PPh3)3Cu2(MoOS3)·0.8 CH2Cl2; 22: (PPh3)3Cu2(WOS3)·0.8 CH2Cl2; 23: {Cu3MoS3Br}(PPh3)3O·0.5Me2CO; 24: (PPh3)3Ag2(WSe4)·0.8 CH2Cl2; 25: [(Ph3P)2N]2(NEt4)2[Fe2S2(WS4)2]·3MeCN; 26: (PPh4)2[MoO(MoS4)2]; 27: (PPh4)2[Br2Fe(WOS4)]·DMF.

Schwingungsspektren und strukturchemie von heterometall-komplexen und -clustern mit thiometallat-liganden

Abstract The thioanions of the early transition metals, e.g. MoOS 3 2− , WOS 3 2− , MoS 4 2− and WS 4 2− , form hetero-metal complexes, which are interesting because of their electronic properties and their relevance to problems of bioinorganic chemistry. Their vibrational spectra are discussed in relation to the molecular structure of the compounds and especially to the wide variety of the coordination types of the thiometalate ligands. It is demonstrated that vibrational spectroscopy (especially Raman and resonance Raman) is a powerful tool for the determination of the local symmetry of the thioanions in polynuclear coordination compounds.

Electron delocalization in thiometallato complexes and clusters with different M′S2MS2 (M′ = Fe, Ag; M = Mo, W) units studied by means of resonance—Raman spectroscopy☆

Abstract Raman and resonance-Raman spectra of [Fe(WS4)2]3−, (PPh4)Fe(MS4) (M = Mo, W), [Fe(H2O)2(WS4)2]2−, [Fe2S2(WS4)2]4−, [Fe3S2(WS4)3]4−, [NCAg(MoS4)]2−, [Ag(MoS4)2]3− and (PPh4)Ag(MoS4) have been measured using different laser lines. The results have been discussed in the light of Fe(Ag) → MS4 electron delocalization which is of considerable bioinorganic interest with respect to the nitrogenase problem.

Notizen: Zum Verständnis der zentralen Rolle des Schwefels in Multi-Metall-Aggregaten mit verschiedener Elektronenpopulation: [S2WS2CoS2WS2]n- (n = 2, 3)/On the Central Role of Sulfur in Multi Metal Aggregates with Different Electron Populations: [S2WS2CoS2WS2]n-(n = 2, 3)

Abstract The hetero metal sulfur aggregates [Co(WS4)2] n- (with variable electron population: n = 2, 3) could be isolated as salts and characterized by physical measurements (in-cluding X-ray structure analysis). Experimental and theoretical investigations show that due to a strong metal → ligand electron delocalisation WS42-(like MOS42-) is a non-innocent ligand and that the additional charge upon reduction is located mainly at the S atoms of the ligand system.