849337-83-3

Upstream product

• 55780-89-7 [(MoO(diethyldithiocarbamate)(μ-O))2] 
• 622-58-2 p-Tolylisocyanate 

Downstream Products

• 849337-89-9 [Mo2(N-p-tol)2(μ-N-p-tol)(μ-PhNC(O)N-p-tol)(S2CNEt2)2] 
• 849338-00-7 [Mo2(N-p-tol)2(μ-S)2(S2CNEt2)2] 
• 849355-74-4 [Mo2(N-p-tol)2(μ-S)(μ-PhNC(O)N-p-tol)(S2CNEt2)2] 
• 849337-86-6 [Mo2(N-p-tol)2(μ-S)(μ-N-p-tolC(O)N-p-tol)(S2CNEt2)2] 

Relevant academic research and scientific papers

Regioselective and reversible carbon-nitrogen bond formation: Synthesis, structure and reactivity of ureato-bridged complexes [Mo2(NAr) 2(μ-X){μ-ArNC(O)NAr}(S2CNR2) 2] (Ar = Ph, p-tol; X = S, NAr; R = Me, Et, Pr)

Reaction of ArNCO with syn-[MoO(μ-O)(S2CNR2)] 2 or syn-[MoO(μ-NAr)(S2CNR2)]2 at 110°C leads to the facile formation of bridging ureato complexes [Mo 2(NAr)2(μ-NAr){μ-ArNC(O)NAr}(S2CNR 2)2] (Ar = Ph, p-tol; R = Me, Et, Pr), formed upon substitution of all oxo ligands and addition of a further equivalent of isocyanate across one of the bridging imido ligands. Related sulfido-bridged complexes [Mo2(NAr)2(μ-S){μ-ArNC(O)NAr}(S 2CNR2)2] have been prepared from syn-[Mo 2O2(μ-O)(μ-S)(S2CNR2) 2]. When reactions with syn-[MoO(μ-NAr)(S2CNEt 2)]2 were followed by NMR, intermediates were observed, being formulated as [Mo2O(NAr)(μ-NAr){μ-ArNC(O)NAr}-(S 2CNEt2)2], which at higher temperatures convert to the fully substituted products. A crystallographic study of [Mo 2(N-p-tol)2(μ-S){μ-p-tolNC(O)N-p-tol}(S 2CNPr2)2] reveals that the bridging ureato ligand is bound asymmetrically to the dimolybdenum centre - molybdenum-nitrogen bonds irons to the terminal imido ligands being significantly elongated with respect to those cis - a result of the trans-influence of the terminal imido ligands. This trans-influence also leads to a trans-effect, whereby the exchange of aryl isocyanates can occur in a regioselective manner. This is followed by NMR studies and confirmed by a crystallographic study of [Mo2(N-p- tol)2(μ-N-p-tol)-{μ-p-tolNC(O)NPh}(S2CNEt 2)2] - the PhNCO occupying the site trans to the terminal imido ligands. Ureato complexes also react with PhNCS, initially forming [Mo2(NAr)2(μ-S){μ-ArNC(O)NAr}(S2CNR 2)2], resulting from exchange of the bridging imido ligand for sulfur, together with small amounts of [Mo2(NAr) 2(μ-S)(μ-S2)(S2CNEt2) 2], containing bridging sulfide and disulfide ligands. The ureato complexes [Mo2(NAr)2(μ-S){μ-ArNC(O)NAr}-(S 2CNR2)2] react further with PhNCS to give [Mo2(NAr)2(μ-S)2(S2CNR 2)2]n (n = 1, 2), which exist in a dimer-tetramer equilibrium. In order to confirm these results crystallographic studies have been carried out on [Mo2(N-p-tol)2(μ-S) (μ-S2)(S2CNEt2)2] and [Mo 2(N-p-tol)2(μ-S)2(S2CNPr 2)2]2. The Royal Society of Chemistry 2005.