174281-06-2

Upstream product

• 147-84-2 Diethyldithiocarbamic acid 
• 259267-48-6 [MoCl₂(NC₆H₄CH₃)2(CH₃OCH₂CH₂OCH₃)] 
• 19680-83-2 bis(N,N-diethyldithiocarbamato)dioxomolybdenum(VI) 
• 614-68-6 2-tolyl isocyanate 

Relevant academic research and scientific papers

Bent vs. linear imido ligation at the octahedral molybdenum(VI) dithiocarbamate stabilised centre

Molybdenum(VI) bis(imido) complexes [Mo(NR)2(S2CNEt2)2] 3a-3p have been prepared via two synthetic routes and their structures investigated. Thermolysis of [MoO2(S2CNEt2)2] 1 with 2,6-disubstituted aryl isocyanates affords air-stable bis(imido) complexes 3i-3m in high yields after column chromatography, a route which fails for sterically less demanding isocyanates. A more general preparation involves room temperature addition of two equivalents of [S2CNEt2]- to the labile bis(imido) complexes [Mo(NR)2Cl2(dme)] 2a-2p (dme = 1,2-dimethoxyethane) to afford 3a-3p in high yields. In this manner related complexes [Mo(NR)2(S2CNMe2)2] 4 (R = Ph or But) and [Mo(NPh)2(S2PPh2)2] 5a have also been prepared. Structural and spectroscopic studies have been carried out in order to determine the degree of bending of the imido ligands. Six complexes have been characterised by X-ray crystallography. In all cases one of the imido ligands is linear (Mo-N-C ≥ 160°), while the angle at the second is dependent upon the nature of R and ranges from 180 to 139°. Solid-state 13C CPMAS spectroscopy reveals that the difference in bond angles at the two nitrogen centres (Δ°) correlates closely with the difference in chemical shifts of the ipso-carbon atoms (Δδ). This then has been used to probe the relative bond angles at nitrogen for non-crystallographically characterised complexes. In solution even at low temperatures both imido ligands are equivalent indicating a rapid interconversion between linear and bent bonding modes. The Royal Society of Chemistry 1999.

Molybdenum(VI) imidodisulfur complexes formed via double sulfur-carbon bond cleavage of dithiocarbamates

Thermolysis of the bis(oxo) complexes [MoO2(S2CNR′2)2] 1 with organic isocyanates afforded imidodisulfur complexes [Mo(NR)(η2-S2)(S2CNR′ 2)2] 2 in moderate yields. Three of the latter, [Mo(NPh)(η2-S2)-(S2CNEt2) 2] 2a, [Mo(NBut)(η2-S2)(S2CNMe 2)2] 2j and [Mo(NC6H3Pri2-2,6)(η 2-S2)(S2CNMe2)2] 2k have been characterised by X-ray crystallography. All contain a distorted pentagonal-bipyramidal metal centre, the disulfur ligand lying in the equatorial plane while the linear imide ligand occupies an axial site. Reaction of 2a with P(OEt)3 afforded the dinuclear molybdenum(V) complex [Mo2O2(μ-NPh))μ-S)(S2CNEt 2)2] 3 which has also been crystallographically characterised. Thermolysis of 2a with an excess of the activated alkyne dimethyl acetylene dicarboxylate yielded three isomeric insertion products formulated as [Mo{SC(R)=C(R)NPh}-{η4-SC(R)=C(R)C(NEt2)S}(S 2CNEt2)] 4 and 5 (differing in the relative orientations of sulfur) and [Mo{SC(R)=C(R)NPh} {η3-SC(R)=C(R)SC(NEt2)}(S2CNEt 2)] 6 (R = CO2Me). The nature of the sulfur-carbon bond cleavage reaction was investigated in a series of experiments centred around the formation of 2a which is concomitant with that of [{MoO(μ-NPh)(S2CNEt2)}2] 7a. Thermolysis of [MoO2(S2CNEt2)2] 1a alone afforded the known molybdenum(V) complex [Mo2O2(μ-O)(μ-S)(S2CNEt2) 2] and, while addition of PhNCO to [MoO(η2-S2)(S2CNEt2) 2] afforded 2a, imido substitution was not noted with Bu1NCO, thus ruling out the general intermediacy of [MoO(η2-S2)(S2CNEt2) 2] in the dithiocarbamate cleavage process. Thermolysis of bis(imido) complexes [Mo(NR)2(S2CNEt2)2] 8 (R = Ph or C6H4Me-o) did not afford the respective disulfur complexes, however thermolysis of [MoO(NPh)(S2CNEt2)2] did give 2a and 7a, thus implicating the oxoimidomolybdenum(VI) complexes as key reaction intermediates. These observations allow a general reaction scheme to be formulated.