Unusual Thermal Reactivity of [W(CPh)(NCMe)(η²‐C₆₀)(η⁵‐C₅Ph₅)] in Chlorobenzene Involving Activation of All Ligands

Abstract

Rummel um Wolfram: Das Erhitzen von 1 in Chlorbenzol liefert 2, 3, C6Ph6 und C60. Bei diesem Prozess werden C‐H‐Bindungen der Liganden aktiviert und neu gebildet, und Chloratome des Lösungsmittels werden abgespalten. C6Ph6 resultiert vermutlich aus dem Einschub des Benzylidinliganden in den C5Ph5‐Ring. Im Produkt 3, einer luftstabilen 17‐Elektronen‐Spezies, bindet der Phenyldichlormethyl‐Ligand im η3‐Modus nach Art eines Allylliganden.

Carbon Modifications and Surfaces for Catalytic Organic Transformations

“…The oxazoline moieties are formed between malonate-terminated Bingel fullerenes and ( R )-phenylalanine to result in C 60 derivative 43 , carrying three chiral bis(oxazoline) ligands. Many single metal coordinates of fullerenes have been recently reported in the literature (e.g., W(CPh)(NCMe)(η 2 -C 60 )(η 5 -C 5 Ph 5 ) 44 ) . In general, investigating the reactivity of fullerene-bound organometallics has become an attractive research topic, , but applications within catalysis remain scarce.…”

Harnessing the Synergistic and Complementary Properties of Fullerene and Transition-Metal Compounds for Nanomaterial Applications

“…The metals which can be attached in an η 2 fashion to the [5,6] or [6,6] bond of the fullerene cage consist mainly of the zerovalent second-and third-row transition metals or metal clusters such as W, 30,38,39 Mo, 29 Pd, 34−36 Pt, 37,44 Rh, 31,33 Ir, 32 Re, 40 and Os, 41−43 with only Co 24,25 and Ni 26−28 represented from the first row. An example of a 1:1 fullerene−metal complex is presented in Figure 3, showing an Ir complex containing an enantiomeric phosphine ligand, resulting in an optically active compound.…”

“…An example of a 1:1 fullerene−metal complex is presented in Figure 3, showing an Ir complex containing an enantiomeric phosphine ligand, resulting in an optically active compound. 32 Late transition metals reported to be attached in the η 2 fashion are typically catalytically active, showing activity in various reactions; for example, both palladium and rhodium fullerene complexes are observed to promote acetylenic bond hydrogenation, 33,34 and a tungsten fullerene complex was found to induce interligand alkyne−alkyne coupling and alkyne scission reactions 38 as well as C−H bond activation and C−C bond formation, 39 which suggests potential applications in catalytic alkyne oligomerization and metathesis reactions. Such compounds also possess rich electrochemical properties, showing several reduction and oxidation waves in cyclic voltammetry corresponding to fullerene-cage-based reductions and metalbased oxidations.…”