Desulfurisation of trithiocarbonates at a dimolybdenum centre: an unexpected insertion into a co-ordinated alkyne

Deconstruction of cyclic and acyclic trithiocarbonates by C–S and CS bond cleavage during oxidative decarbonylation of dimolybdenum alkyne complexes †

“…Analogous products 9 and 10 were formed in crystallised yields of 44 and 54% respectively. 8 Their characterising data are unremarkable in the light of the structure of 8. One interesting feature however is that all three compounds display FAB mass spectra consisting of an envelope of peaks corresponding to the molecular ion and a second which corresponds to the loss of C 2 R 2 , i.e.…”

“…It appears that all three sulfur atoms of the trithiocarbonate group are required for successful reaction as other related heterocycles containing O or NPr i in place of S did not give any tractable products. 8 The effect of changing the alkyne ligand was also explored. Complexes 2 (R 1 = R 2 = CO 2 Et) and 3 (R 1 = R 2 = Ph) both reacted successfully with heterocycle 5 to give compounds 11 (69%) and 12 8 (20%) respectively.…”

“…8 The effect of changing the alkyne ligand was also explored. Complexes 2 (R 1 = R 2 = CO 2 Et) and 3 (R 1 = R 2 = Ph) both reacted successfully with heterocycle 5 to give compounds 11 (69%) and 12 8 (20%) respectively. Complex 4, containing the unsymmetrical alkyne PhC᎐ ᎐ ᎐ CCO 2 Et, also reacted to give two isomeric products 13 and 14 in which the thione is coupled to the CCO 2 Et or the CPh terminus of the alkyne respectively.…”

“…This paper reports the results obtained with various cyclic and acyclic trithiocarbonates, and amplifies the accounts given in two preliminary communications. 8 † Electronic supplementary information (ESI) available: elemental analysis data. See http://www.rsc.org/suppdata/dt/b0/b004293p/…”

Wraparound ligands: addition of activated alkynes to sulfur- and thiolate-bridged dimolybdenum complexes derived from trithiocarbonates

“…5 In the case of simple acyclic trithiocarbonates such as dimethyl trithiocarbonate a similar product was obtained, though with the additional novel feature that the C(SMe) group had effectively become inserted into the alkyne rather than occupying a terminal position in the dimetallaallyl unit. 6 These products form the starting point for the further reactions described in this paper.…”