RESUMO
Synthesis of stable irida-binaphthyl and -phenanthryl complexes, the first examples of metallaaromatic biaryl atropisomers, has been achieved. The combination of experimental and theoretical studies revealed that the nature of these systems is comparable to that of well-known 1,1'-binaphthalene both in terms of aromaticity and atropisomerism.
RESUMO
A methoxy(alkenyl)carbenerhodium complex [RhCp*Cl{[double bond, length as m-dash]C(OMe)CH[double bond, length as m-dash]CPh2}(PMe3)]PF6 (2) has been synthesized and used as the starting material for the study of the effect of the metal center (Rh vs. Ir) in the formation of new rhodacycle complexes. While η3 and η5 indenylrhodium complexes have been achieved by the C-H bond activation of a phenyl ring, insertion of terminal alkynes into the rhodium-carbene bond led to the first example of the synthesis of rhodafuran complexes through rhoda-1,3,5-hexatriene intermediates. This new method represents an efficient process to obtain metallafuran complexes.
RESUMO
Iridanaphthalene complexes are synthesized from the corresponding methoxy(alkenyl)carbeneiridium compounds. The electronic character of the substituents on the 6-position of the metallanaphthalene ring is crucial from the point of view of the stability of the iridanaphthalene, [Ir[upper bond 1 start]Cp*{=C(OMe)CH=C(o-C[upper bond 1 end]6H4)(Ph)}(PMe3)]PF6, vs. its transformation to the corresponding indanone derivatives. Stability studies of the iridanaphthalene compounds revealed that strong electron donor substituents (-OMe) stabilize the iridanaphthalene, while weak electron donor (-Me) and electron withdrawing (-NO2) groups favor the formation of indanone derivatives. Two possible indanone isomers can be obtained in the conversion of the unstable iridanaphthalene complexes and a mechanism for the formation of these isomers is proposed.