Synthesis, reactivity, and structures of cationic ? 6-arene carbonyl complexes of rhenium(I). Crystal and molecular structures of the two isoelectronic 1,3,5-trimethylbenzene tricarbonyl complexes of rhenium(I) and tungsten(0)

Fausto Calderazzo (1) , Rinaldo Poli (1) , Aldo Barbati (1) , Pier Francesco Zanazzi (2)

1 University of Pisa - Università di Pisa
2 UNIPG - Università degli Studi di Perugia = University of Perugia

Cationic arene derivatives of tricarbonylrhenium(I), less methyl substituted than hexamethylbenzene, of general formula [Re(CO)3{C6H6–n(CH3)n}]+ with [AlBr4]–, [BPh4]–, or [Re2l8]2– as counter anion, have been isolated. The crystal and molecular structure of the trimethylbenzene complex [Re(CO)3{1,3,5-C6H3(CH3)3}][AlBr4] has been solved by X-ray diffraction methods: monoclinic, space group P21/a, with unit-cell dimensions a= 15.687(3), b= 12.876(3), c= 9.690(2)Å, β= 101.95(2)°, and Z= 4; R= 0.046 for 1 220 observed reflections. The corresponding neutral tungsten(0) complex [W(CO)3{1,3,5-C6H3(CH3)3}] is monoclinic, space group P21/a, with unit-cell dimensions a= 8.959(2), b= 16.979(3), c= 8.797(2)Å, β= 118.46(2)°, and Z= 4; R= 0.036 for 861 observed reflections. Both complexes have an eclipsed orientation of the carbonyl groups with respect to the methyl substituents on the ring. Reduction of [Re(CO)3{1,3,5-C6H3(CH3)3}]+ with [BH4]– afforded the trimethyl-substituted cyclohexadienyl complex, [Re(CO)3{1,3,5-C6H4(CH3)3}].

Domaines: Chimie de coordination; Cristallographie

Fausto Calderazzo, Rinaldo Poli, Aldo Barbati, Pier Francesco Zanazzi. Synthesis, reactivity, and structures of cationic ? 6-arene carbonyl complexes of rhenium(I). Crystal and molecular structures of the two isoelectronic 1,3,5-trimethylbenzene tricarbonyl complexes of rhenium(I) and tungsten(0). Journal of the Chemical Society Dalton Transactions, 1984, 6, pp.1059-1064. ⟨10.1039/DT9840001059⟩. ⟨hal-03545451⟩