165287-44-5

Upstream product

• 55780-89-7 [(MoO(diethyldithiocarbamate)(μ-O))2] 
• 614-68-6 2-tolyl isocyanate 
• 167224-82-0 [(MoO(diethyldithiocarbamate)2(μ-NC6H4Me-o))2] 
• 19680-83-2 bis(N,N-diethyldithiocarbamato)dioxomolybdenum(VI) 

Relevant academic research and scientific papers

Synthesis and structural characterisation of the dimeric tetraimido complex [Mo(N-o-tolyl)(η2-S2CNEt2)(μ-N-o-tolyl)]2

Thermolysis of a slight excess of o-tolylisocyanate with either [MoO2(η2-S2CNEt2)2] or [MoO(η2-S2CNEt2)(μ-O)]2 afforded the tetraimido complex [Mo(N-o-tolyl)(η2-S2CNEt2)(μ-N-o-tolyl)]2 characterisedby X-ray crystallography in the solid state and which exists as a mixtu re of interconverting rotomers in solution due to restricted rotation about the nitrogen-carbon bond of the imido ligands.

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.

Synthesis and Structural Characterisation of Dithiocarbamate-stabilised Dimeric Molybdenum(V) Imido Complexes via Oxo Substitution Reactions with Organic Isocyanates

Thermolysis of molybdenum-oxo complexes 1, 2> 2 and 3 with organic isocyanates afforded a range of imido-substituted binuclear molybdenum(V) complexes.Reaction of complex 1 with 1 equivalent of RNCO gave terminally substituted mono(imido) complexes 4a-4c (R = t-Bu, 2,6-Me2C6H3 or adamant-1-yl) and bridging bis(imido) complexes 2> 5a and5c (R = Ph or p-tolyl).Reaction of complex 2 with an excess of RNCO afforded the tetraimido complex 2> 6b (R = o-tolyl) and the bridging ureato complex > 7a, while with PhNCO and complex 3 a further ureato complex > 7b resulted.Thermolysis of complex 7a gave the tetraimido complex 2> 6a, a reaction which is reversed in the presence of PhNCO.Acid-catalysed hydrolysis of complex 6b afforded the bis(imido) complex 2> (R = o-tolyl) 5b which upon thermolysis with o-tolyl isocyanate regenerated 6b.Addition of HBF4 to 5a resulted in oxo substitution by dithiocarbamate to give 8.Six of these complexes, namely 4a, 4b, 5b, 6b, 7a and 8, have been characterised by X-ray crystallography.All are dimeric and contain relatively short molybdenum-molibdenum contacts (2.625-2.822 Angstroem) indicative of metal-metal bonding, the longer distances being associated with bridging sulfido ligands.Terminal imido ligands are all linear and bridging imido ligands planar.