Re–Re bond breaking of (μ-H)₃Re₃(CO)₁₁(NCMe) upon reaction with PPh₂(o-C₆H₄)(CH₂NMeCH)C₆₀to generates monorhenium and dirhenium phosphino–fullerene complexes

Abstract

Reaction of PPh(2)(o-C(6)H(4))(CH(2)NMeCH)C(60) (1) and (μ-H)(3)Re(3)(CO)(11)(NCMe) in refluxing chlorobenzene affords the monorhenium complex HRe(CO)(3)(η(3)-PPh(2)(o-C(6)H(4))(CH(2)NMeCH)C(60)) (2), and the dirhenium complexes (μ-H)Re(2)(CO)(7)(μ,η(3)-PPh(o-C(6)H(4))(2)(CH(2)NMeCH)C(60)) (3) and (μ-H)Re(2)(CO)(5)(μ-SSOH)(μ,η(5)-PPh(2)(o-C(6)H(4))(CH(2)NMeCH)C(60)) (4). The structures of 2-4 have been determined by an X-ray diffraction study. The oxatrisulfanyl (-SSOH) ligand of 4 likely arises from decomposition of CS(2) on silica gel during the purification processes.

Reversible C–C bond formation at a triply cyclometallated platinum(iv) centre

“…Nine-membered rings have considerable precedence in the literature, though there are only seven crystal structures of transition metal complexes with one P and one N donor reported; of these, six are of chiral spiro iridium phosphine complexes used for enantioselective transformations 23 and the last one is of a dirhenium phosphino-fullerene. 24 There are rather more nine-membered rings where both donors to the metal are nitrogen. In some of the crystal structures of these κ 2 N donors the donors span trans 25 coordination sites, some cis 26 and there is one example where a change from trans to cis occurs upon addition of CO. 27 The formation of the eight-membered linkage that becomes the nine-membered metallacycle from two equal sized rings does not appear to have been seen before with two different cyclometallated ligands (as in the phosphine and pyridine reported here), but has been seen with two identical ligands.…”

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

“…P-donor diphenylphosphine was successfully attached to fullerene to form a new class of compounds with the formula C 60 (H)­PPh 2 that can coordinate heavy second- and third-row transition metals in what is formally an η 3 mode involving the electron pair of the phosphorus atom and the π–π system of one or more of the C–C bonds of the fullerene cage (Figure , compound 97 ). − These complexes have been reported to catalyze a variety of reactions in which the activity and selectivity of the reaction can be controlled by the steric and electronic effects of the substituents at the phosphorus atom. C 60 (H)­PPh 2 has also been used to act as a redox-active unit which when attached to a model [FeFe]­hydrogenase core can mimic the activity of the hydrogenase enzyme (Figure , compound 98 ). , These complexes exhibit extensive electron communication in the doubly reduced state between the reduced fullerene cage and the Fe 2 centers.…”

Synthesis and characterization of a trans-1 hexakis-fullerene linker that forms crystalline polymers with silver salts

“…Fullerene derivatives possess unique physicochemical properties and have potential applications as electronic, magnetic, catalytic, biological and optical materials. [1][2][3][4][5][6][7][8][9][10] The three-dimensional structure of the carbon sphere and the multiple reactive bonds on C 60 make it an ideal candidate as a building block for the construction of interesting and functional supramolecular architectures. 11,12 So far, the synthesis of fullerene-based coordination polymers has been reported in only a few cases.…”