Molybdenum complexes thiolates

The molybdenum neopentyUdene complex Mo(CHBu )(NR)(OBu )2 is the active catalyst used in a fascinating development for the synthesis of 11-Vt semiconductor clusters (ZnS, CdS, PbS) and silver and gold nanoclusters of predictable size within microdomains in films of block copolymers prepared by ROMP. Block copolymers of norbomene and a functionalized norbomene that wiU complex with a metal-containing compound were prepared and characterized as monodisperse materials. The functionalized component (amine, alkoxide, or thiolate) then sequestered the metal and the metallated block copolymer was cast into a film which was subsequently treated with H2S to convert the metal into the sulfide. The molybdenum complexes have also featured in the development of the synthesis of side-chain liquid crystal polymers by living ROMP.98 99... 

The bulky thiolate ligand 2,4,6-triisopropylbenzenethiolate (tipt) forms the stable complex [Mo(tipt)4], which gives monoadducts with alkynes, nitriles, CO and other small ligands and, unlike [Mo(SBu )4], the molybdenum does not appear to be reduced in these reactions.182... 

The extent of alkyne ir donation in Mo(RC=CR)(SBu )2(CNBu% (SO) is not easily quantified as discussed in the structural and molecular orbital sections. Proton shifts for HC=CH and PhC=CH ligands in these complexes are near 10.4 ppm, above the N = 4 median value and approaching an N = 3 chemical shift. The 13C chemical shifts range from 170 to 185 ppm, also above classic four-electron donor alkyne values, presumably reflecting competition with the two adjacent equatorial thiolates for donation to the two vacant metal dir acceptor orbitals. Single bond VCH values of 215 and 211 Hz are typical of terminal alkynes bound to molybdenum(II) (133). 

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