Coordination and Rearrangement of Organic Chalcogenides on a Rhodium−Rhodium Bond:  Reactions with Strained-Ring Cyclic Thioethers and with Selenium and Tellurium Ligands

Abstract

When the cyclic thioethers L = and were added to [(η5-C5H5)2Rh2(μ-CO)(μ-η2:η2-CF3C2CF3)] (1), the coordinative addition products [(η5-C5H5)2Rh2(CO)(μ-η1:η1-CF3C2CF3)L] (2a−c) were formed reversibly. When it is left in solution in the presence of excess ligand, the propylene sulfide complex 2b (L = transforms to the bridging sulfido complex [(η5-C5H5)2Rh2{μ-η1:η1:η2-C(O)C(CF3)C(CF3)}(μ-S)] (3a). A similar reaction occurred, but to a lesser extent, with the trimethylene sulfide complex 2a (L = Comparable decompositions do not occur with the tetrahydrothiophene complex 2a (L = The dimethylselenane complex [(η5-C5H5)2Rh2(CO)(μ-η1:η1-CF3C2CF3)(SeMe2)] (4a) was formed reversibly when SeMe2 was added to solutions of 1. The reactions of 1 with the organotelluranes L‘ = TeMe2 and TeEt2 gave solid addition products [(η5-C5H5)2Rh2(CO)(μ-η1:η1-CF3C2CF3)L‘] (4b,c), which remained intact when dissolved in polar solvents. No rearrangement products were formed when solutions of the tellurane addition products were kept for several days. The bridging sulfido complex 3a and the analogous complexes [(η5-C5H5)2Rh2{μ-η1:η1:η2-C(O)C(CF3)C(CF3)}(μ-E)] (3b, E = Se; 3c, E = Te) were obtained from the direct reaction between E and the complex 1. Addition of the cyclic tellurane to 1 gave (6), which underwent rapid intramolecular ligand scrambling in solution. The crystal and molecular structure of 6 was determined by X-ray crystallography.

Emerging trends in organotellurolate chemistry derived from platinoids

“…The reaction of TeR 2 (R ¼ Me, Et) with metallocyclic [(C 5 H 5 ) 2 Rh 2 (m-CO)(CF 3 CCF 3 )] derived an adduct in which TeR 2 was added to one of the rhodiums attached with bridging carbonyl, which was boned in a h 1 fashion. 69 Such a type of insertion followed by the addition of tellurium can be particularized due to diffusive sets of lone pairs and their ease of availability to coordination. While the reaction of RhCl The uxional behavior of the latter complex was established by its 1 H NMR spectrum, which showed a single resonance for TeMe, CH 2 , and COD (Scheme 3).…”

“…Compared to other platinoids, a signicant amount of work has been documented on Pd(II) and Pt(II) complexes derived from telluroethers. [65][66][67][68][69] Among these cyclic complexes, [MX 2 {Te(CH 2 ) 4 } 2 ] (M ¼ Pd, Pt; X ¼ Cl, Br, I) has been isolated from the reaction with cyclic telluroethers, i.e., telluracyclopentane Te(CH 2 ) 4 . 72 In the case of the platinum metal system, both cis-and trans-congured complexes have been reported.…”

Dichalcogenide Cleavage and Carbonyl Insertion Reactions on a Dirhodium Bond

“…Previously, we have shown that the reaction of dialkyl sulfides, SRRЈ to [(η-C 5 H 5 ) 2 Rh 2 (μ-CO)(μ-η 2 :η 2 -C 2 (CF 3 ) 2 )] (1) proceeded by coordination of the sulfide [19,20] and giving [(η-C 5 H 5 ) 2 Rh 2 (μ-CO)(μη 1 :η 1 -C 2 (CF 3 ) 2 )(SRRЈ)], a reaction which was reversible. On prolonged contact with SR 2 (R ϭ Me, Et) interesting transformations occurred, giving [(η-C 5 H 5 ) 2 Similarly reaction of 1 with a strained cyclic thio-, selenoand telluro-ether compounds gave the addition products (analogous to 2) reversibly in the first instance [18], but work-up of solutions containing excess cyclochalcoether gave complexes 5. These complexes can also be prepared by the reaction of the elements [18] with 1; in the case of elemental Se another isomer 6 was isolated, the structure sharing a similarity with complexes 4.…”

“…On prolonged contact with SR 2 (R ϭ Me, Et) interesting transformations occurred, giving [(η-C 5 H 5 ) 2 Similarly reaction of 1 with a strained cyclic thio-, selenoand telluro-ether compounds gave the addition products (analogous to 2) reversibly in the first instance [18], but work-up of solutions containing excess cyclochalcoether gave complexes 5. These complexes can also be prepared by the reaction of the elements [18] with 1; in the case of elemental Se another isomer 6 was isolated, the structure sharing a similarity with complexes 4.…”

Versatile coordination chemistry of rhodium complexes containing the bis(trimethylsilylmethyl)tellane ligand

“…Of the few known crystal structures of mononuclear rhodium complexes that contain telluroether ligands [9][10][11][12][13], [RhCp * L][PF 6 ] 2 {L = MeS(CH 2 ) 3 Te((CH 2 ) 3 SMe)} is of special interest, since L acts as a tridentate ligand with one Te and two S donor atoms [13]. To our knowledge, no crystal structures of such hybrid rhodium complexes containing discrete thioether and telluroether ligands have hitherto been reported.…”