Hydroxylamido(1‐)‐O,N‐Komplexe des Molybdäns(VI) mit terminalen Oxo‐, Sulfido‐ und Selenido‐Liganden Die Kristallstrukturen von [MoO₂(C₅H₁₀NO)₂] und von [MoS₂(C₅H₁₀NO)₂]

Abstract

Die Neutralkomplexe cis‐Dioxo‐bis(hydroxylamido(1‐)‐O, N)molybdän(VI) mit O,N‐koordinierten, N,N‐substituierten Hydroxylamin‐Liganden reagieren mit H2S in Toluol unter Substitution einer oder beider terminaler Oxo‐Gruppen zu cis‐Oxosulfido‐ bzw. cis‐Disulfido‐bis(hydroxylamido(1‐)‐O, N)molybdän(VI)‐Komplexen; mit H2Se entstehen die entsprechenden cis‐Oxoselenido‐Komplexe. Die Kristallstrukturen der Titelverbindungen mit Piperidin‐N‐oxid als Ligand werden beschrieben: Der cis‐Disulfido‐Komplex kristallisiert tetragonal in der Raumgruppe D 2d11—I 4 2 m mit vier Formeleinheiten i. d. Elementarzelle; die analoge cis‐Dioxo‐Verbindung kristallisiert orthorhombisch (D 24—P212121) mit 4 FE i. d. EZ. Die 1H—NMR‐Spektren sowie die Lichtabsorptionsspektren werden mitgeteilt.

Facets of early transition metal–sulfur chemistry: Metal–sulfur ligand redox, induced internal electron transfer, and the reactions of metal–sulfur complexes with alkynes

“…However, the combination of oxidizing Mo(VI) and reducing sulfido moieties is difficult to achieve due to redox reactions that generally produce bi-or polynuclear l-sulfido-Mo(V) species [33]. The direct conversion of oxo-Mo(VI) complexes into sulfido-Mo(VI) complexes is limited to tetrahedral or pseudo-tetrahedral species such as thiomolybdates [34], MoOS(ONR 2 ) 2 (R = alkyl) [35,36] and Cp * MoOS(CH 2 SiMe 3 ) [37]. Attempts to convert octahedral oxo-Mo(VI) complexes into sulfido analogues usually result in reduction or polysulfido ligand formation, an example being the generation of the tetrasulfido-Mo(IV) complexes, Tp * MoX(S 4 ), discussed in Section 2.1.…”

“…The vinyl sulfide (35), vinyl disulfide (36) and trithiolene (37) ligands are only sparsely represented due to their ready transformation into the more stable dithiolene ligand (38) [17]. The reactions of alkynes with metal complexes containing organosulfur ligands are generally more complicated, producing a number of intriguing species en route to dithiolene complexes.…”

“…(35), a reaction that has been known for over four decades [159]. We close this section by describing Wang and Stiefel's novel Ni dithiolene-based separation of olefins [87,160].…”

First Dioxomolybdenum(VI) Complexes Containing Chiral Oxazoline Ligands: Synthesis, Characterization and Catalytic Activity

“…1.7 Å in both structures, as reported previously. [14] The distances MoϪN for Λ-N-trans-1 [MoϪN(1) ϭ 2.31 Å and MoϪN(2) ϭ 2.33 Å ] were longer than for ∆-N-cis-1 (MoϪN ഠ 2.15 Å ) due to the oxo trans influence. However, the molybdenum phenolic oxygen lengths either in ∆-N-cis-1 or Λ-N-trans-1 showed a negligible influence of the geometrical arrangement.…”

Inhibition of yeast growth by molybdenum-hydroxylamido complexes correlates with their presence in media at differing pH values

“…Mo complexes with hydroxylamido ligands were chosen for these studies, in part because of the known chemistry of representative simple complexes [7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22], and in part because of their anticipated analogy with their corresponding vanadium-hydroxylamido complexes [16,19,[23][24][25]. The most common bonding modes for hydroxylamines are the end-on and the bidentate modes.…”