Nucleophilic ring opening of bridging thietane ligands in trirhenium carbonyl cluster complexes

Catalytic Macrocyclization of 3-Methylthietane by Re2(CO)9(SCH2CHMeCH2) and W(CO)5(SCH2CHMeCH2)

“…Both molecules are structurally similar, and an ORTEP diagram of the molecular structure of one of them is shown in Figure . The conformation of the 12-membered ring of the macrocycle is virtually identical with that of the free molecule 3 (see above) . The ligand is coordinated to one of the rhenium atoms through one of the two sulfur atoms that lie along the edges of the “square” ring conformation of the ligand: Re(2)−S(1) = 2.506(3) Å [Re(4)−S(4) = 2.510(3) Å].…”

The reaction of [Re2(CO)8(MeCN)2] with thiols. Formation of hydrido sulfido bridged dirhenium cluster complexes [Re2(μ-H)(μ-SR)(CO)8] (R = H, n-Bu, Cy, Ph, C6H4F-p, C6F5 or 2-naphthyl)

“…We were not able to detect 6 by IR spectra of the reaction mixtures. Each spectrum exhib- 13 On the other hand 7 cannot be the intermediate in the reaction between 2a and 1 as the sulfido bridge in 2a has only one free electron pair left. In this case the intermediate 8 with a coordinated S-H bond may be formed.…”

Reactivity of the Anionic Carbonyltrirhenium Cluster [Re3(µ-H)3(µ3-ampy)(CO)9]− − Synthesis of Neutral Phosphane and Alkenyl Derivatives

“…Moreover, [Re 3 (µ-H) 3 12 ] is kinetically very stable and most of its reactions require high temperatures (which promote changes in cluster and/or ligand integrity, often leading to mixtures of products) [1] or derivatization to the more reactive [Re 3 (µ-H) 3 (CO) 10 (MeCN) 2 ]. [7] Ciani, D'Alfonso and co-workers have extensively studied the derivative chemistry of the anionic unsaturated cluster [Re 3 (µ-H) 4 (CO) 10 ] Ϫ , [1] but its best preparation requires a high pressure hydrogenation (100 atm) of [Re 3 (µ-H) 2 (CO) 12 ] Ϫ , [8] Ph; 5: R = RЈ =Et; 6a: R = Ph, RЈ = H; 6b: R = H, RЈ = Ph). In 2 and 3, the phosphane ligand is in an equatorial position on an Re atom of the NH-bridged Re−Re edge, cis to a hydride ligand and far away from the other hydride ion.…”