X‐ray structure investigations of the complexes (III) and (VI), obtained by the title reaction, show that (III) (space group P21/c, Z=4) contains a "side‐on" bound hydrazido(1‐) ligand NH2NC(O)SMe, whereas in (VI) (space group P1, Z=1) the same ligand is N,O‐chelated.
Die Reaktion von NH2NHC(O)SMe mit MoO2(S2CNEt2)2 und MoO2(ONEt2)2 ergibt die Diazenido‐Hydrazido‐Komplexe [Mo(NNC(O)SMe)(NH2NC(O)SMe)(S2CNEt2)2] · CH2Cl2 (2) bzw. [(μ‐OMe)Mo(NNC(O)SMe)(NH2NC(O)SMe)(ONEt2)]2 (4). Röntgenstrukturanalysen von 2 und 4 ergaben, daß der Hydrazido(1 – )‐Ligand NH2NC(O)SMe in 2 symmetrisch “side on”, im dimeren 4 dagegen als N,O‐Chelat gebunden ist. Die Mo–N‐Abstände in 2 betragen 213.1(7) und 213.4(5) pm, der N – N‐Abstand 140.4(9) pm. Die Stickstoffatome sind sp3‐hybridisiert. Mögliche Faktoren für die “side‐on”‐, “end‐on”‐oder chelatartige Koordination von Hydrazido(1 – )‐Liganden werden diskutiert.
(2).The reaction of alkyldithiocarbazates NH2NHC(S)SR′ with MoO2(S2CNR2)2 R, R′ = Me, Et) yields the diazenido hydrazido complexes Mo(NNC(S)SR′)(NH2NC(S)SR′)(S2CNR2)2 (1), reaction with the molybdenum hydroxylamidate complex MoO2(ONMe2)2 gives the diazenidobis( hydrazido) complex Mo(NNC(S)SMe)(NH2NC(S)SMe)2(Me2NO)-CH3OH The crystal structures of 1 a (R = Me, R′ = Et) and 2 have been determined. The metal atoms in 1 a and 2 are seven coordinated and have MoN2S5 and MoN3O2S2 ligand arrays, respectively. Both compounds contain the approximately linear diazenido ligand NNC(S)SR in addition to one (1a) or two (2) N,S-chelating hydrazido(1-) ligands NH2NC(S)SR. When 1a is treated with HCl, the dimeric complex (Me2NCS2)(O)Mo(μ-NNC(S)SEt)2 Mo(S2CNMe2) (4) is obtained. X-ray crystallography showed 4 to be an asymmetric dinuclear complex, with a Mo-Mo distance of 267.2(1) pm. One Mo site has a square pyramidal MoOS2N2 geometry, while the other one has an approximately trigonal prismatic MoN2S4 geometry. The mean N-N distance in 4 is 135(1) pm. The reaction of NH2NHC(S)SMe with MoO2(acac)2 yields Mo(Me2CNNC(S)SMe)(NNC(S)SMe)(MeSC(S)NNC(S)SMe) (3). Its structure has been determined by X-ray crystallography. 3 contains a unique combination of three different N- and S-chelating ligands: the Schiff base Me2C=NNC(S)SMe, the highly bent bidentate diazenido ligand NNC(S)SMe (∡ Mo-N-N = 142.1(5)°), and the novel planar tridentate ligand MeSC(S)NNC(S)SMe. The latter can be taken as neutral diacyldiazene or, more likely, as the dianion of the as yet unknown MeSC(S)NH -NHC(S)SMe. The N - N distance in this ligand is 136.1(9) pm.
Die Reaktion von Me3SiCl mit NH2NHC(S)SMe ergibt als einziges Produkt die Titelverbindung (Me3Si)2NNHC(S)SMe (1). Ihr Molekülgerüst ist nicht planar. Die SiN‐Abstände betragen 176,9(8) bis 178,1(9) pm. 1 reagiert mit Cp2TiCl2, CpTiCl3, MCl5 und CpMCl4 (M = Nb, Ta) nicht zu Hydrazido‐ oder Diazenidokomplexen. Mit MoO2Cl2(dmso)2 wird der dimere Komplex (dmso)2Mo(μ‐NNC(S)SMe)2Mo(O)Cl2 erhalten.
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