96041-49-5

Upstream product

• 27770-63-4 Re₂(CO)9(P(C₆H₅)3) 
• 74-85-1 ethene 
• 101401-60-9 Re₂(CO)8(P(CH₃)3)2 
• 14285-68-8 decacarbonyldirhenium⁽⁰⁾ 

Relevant academic research and scientific papers

Photochemical reactions of Re2(CO)9L, 1,2-Re2(CO)8L2, and Re2(CO)8(μ-L L) with Alkenes

The photochemical reactions of Re2(CO)9L (L = PMe3, PPh3) with ethylene give (μ-H)Re2(CO)8(μ-CH=CH2), (μ-H)Re2(CO)7(μ-CH=CH2)L (1, L = PMe3; 2, L = PPh3) and (μ-H)Re2(CO)6(M-CH=CH2)L2 (3a, L - PMe3; 3b, L = PPh3). There are four isomers each of 1 and 2 relating to the locations of the phosphine ligand. Photolysis of 1,2-Re2(CO)8L2 (L = PMe3, PPh3) in the presence of ethylene yields mainly 3a or 3b. The equivalent reaction of a 3:2 mixture of Re2(CO)10 and 1,2-Re2(CO)8(PMe3)2 yields (μ-H)-Re2(CO)8(μ-CH=CH2) and 1; that of the 1:1 mixture of 1,2-Re2(CO)8(PMe3)2 and 1,2-Re2(CO)8(PPh3)2 gives (μ-H)Re2(CO)6(μ-CH=CH2)(PMe 3)(PPh3) as one of several products. The results are consistent with metal-metal bond cleavage as the important primary photoprocess. The photochemical reactions of Re2(CO)8(μ-dmpm), -(μ-dppe), and -(μ-dmpe) with H2C=CHR (R = H, Me) proceed very slowly to give (μ-H)Re2(CO)6(μ-dmpm)(μ-CH=CHR), 4, (μ-H)Re2(CO)6(μ-CH=CHR)(dppe), 5, and (μ-H)Re2(CO)6(μ-LH=CHR)(dmpe), 6. These reactions appear to proceed mainly by photodissociation of CO. Coordination of dmpe and dppe has undergone rearrangement to a chelate configuration. The μ-alkenyl ligand of 4 undergoes a rapid fluxional process at ambient temperature in which the σ- and π-bonds of the alkenyl group are interchanged between the bridged rhenium atoms.

NOVEL, DINUCLEAR MECHANISM FOR CATALYTIC OLEFIN DIMERIZATION. PHOTOCHEMICAL REACTIVITY OF ( mu -HYDRIDO)( mu -ALKENYL)DIRHENIUM OCTACARBONYL COMPOUNDS.

UV photolysis of ( mu -hydrido)( mu -ethenyl)dirhenium octacarbonyl, ( mu -H)( mu CH equals CH//2)Re//2(CO)//8(I), in the presence of ethylene affords ( mu -hydrido)( mu -butenyl)dirhenium octacarbonyl complexes. A mechanism is proposed in which the initial step is photodissociation of CO from I, as photolysis of I in the presence of **1**3CO or PPh//3 results in CO substitution. Subsequent steps in the formation of the mu -hydrido mu -butenyl species are coordination of ethylene, insertion of ethylene into the Re-H or Re-ethenyl sigma bond, recoordination of CO, C-C or C-H reductive elimination to yield Re//2(CO)//8(1-butene), and oxidative addition of a vinylic C-H bond of coordinated butene.