Cyclopentadienyl dithiocarbamate and dithiophosphate molybdenum and tungsten complexes

Abstract

Reactions of [MCp*Cl 4

Half-sandwich complexes of molybdenum-(III), -(IV) and -(V) with P–O and P–N bifunctional ligands Ph2PCH2X (X = 2-oxazolinyl, or C(O)NPh2)

“…The structure of the cation would be identical to that determined for the cation of compound 7 containing ligand II, see below, whose EPR parameters are essentially identical to those of B and significantly different from those of the reaction intermediate A. Another related structure is that of [MoCp*Cl3{S2P(OEt)2}], 59 where the bidentate dithiophosphate ligand occupies the axial and one of the equatorial positions. The reduction of compound 3 (thermodynamic isomer B) with two equivalents of sodium failed to yield 2 and the characterization of the reduction product was therefore not pursued.…”

“…Calc. for C31H27Cl2MoNOP: C, 59 An analogous preparative procedure was carried out from II (0.590 g, 1.49 mmol) and [MoCp(µ-Cl)2]2 (0.346 g, 0.75 mmol) in 25 mL of CH2Cl2, a difference being that the mixture was stirred overnight. After filtration through Celite, the filtrate was evaporated to dryness and the residue extracted with hot toluene (30 mL) and filtered.…”

Monomeric cyclopentadiene molybdenum oxides and their carbonyl precursors as epoxidation catalysts

“…Faller and Ma were the pioneers in the synthesis of Cp * Mo(O 2 )OCl [10]. Later, Royo et al presented two other alternative synthetic pathways to obtain Cp * -Mo(O 2 )OCl, which could also be applied to obtain CpMo(O 2 )OCl [33]. The molecular structure of CpMo-(O 2 )OCl was determined by X-ray crystallography [34].…”

Oxidation of [CpMo(CO)3R] olefin epoxidation precatalysts with tert-butylhydroperoxide

“…Products of oxidative decarbonylation -Oxomolybdenum (IV,V,VI) complexes I 0 , M ox1, M ox2 , I and IIReaction of Mo(II) tricarbonyl precursors such as 5 with excess TBHP usually results in the formation of relatively stable Mo(VI) dioxo and oxo-peroxo complexes, and several such species have been isolated and identified by X-ray crystallography[10,22,38,[48][49][50]. However, the evidence in favour of I and II does not exclude the possibility of formation and side reactions of intermediate oxo species with oxidation states of Mo as +IV or +V, before the complexes with the highest oxidation state of +VI are obtained.…”