Photochemical CCl bond activation of trichloroarenes by the rhenium complex (η5-C5Me5)Re(CO)3. X-ray structure of trans-(η5-C5Me5)Re(CO)2(2-methoxy-4,5-dichlorophenyl)chloride

Reductive elimination reaction of rhenium complexes trans-(η5-C5Me5)Re(CO)2(chloroaryl)Cl

“…By considering that the Re centre in the starting complexes trans-Cp * Re(CO) 2 (Ar Cl )Cl, is sterically crowded, probably the first step of the reaction should involve the migration of the aryl group to the Cp * ligand with simultaneous reduction of Re(III) to Re(I) to give the unobserved diolefinic intermediate (g 4 Taking into account the results described above and those previously reported for similar complexes, containing different chloroaryl ligands [6][7][8][9] it is clear that the substituents on the aryl ligand plays an important role in deterScheme 1. Thermal reactions of trans-Cp * Re(CO) 2 (Ar Cl )Cl with acetonitrile or trimethylphosphite.…”

“…For several years we have been involved in investigating the C-Cl bond activation of chloroaromatic compounds from the photogenerated rhenium fragment Cp * Re(CO) 2 [6][7][8][9]. We have successfully achieved the insertion of the rhenium fragment in a quite large number of chlorobenzene [6,7] and chloroarene [8,9] molecules to form complexes, possessing a ''four legged piano-stool'' type of structure with a general formula Cp * Re(CO) 2 (Ar Cl )Cl.…”

“…We have successfully achieved the insertion of the rhenium fragment in a quite large number of chlorobenzene [6,7] and chloroarene [8,9] molecules to form complexes, possessing a ''four legged piano-stool'' type of structure with a general formula Cp * Re(CO) 2 (Ar Cl )Cl. Since in most of the cases, the isolated products possess a trans stereochemistry and considering the current interest on the cis M trans isomerization reactions of complexes of the type CpML 2 L 0 2 , both in solution [10] and confined environments [11], we undertook a research program to study the experimental conditions which allow us to achieve trans to cis isomerization of the complexes transCp * Re(CO) 2 (Ar Cl )Cl (Ar Cl = 3-ClC 6 H 3 (4-Me) [9], 3,5-Cl 2 C 6 H 3 [7] and 3-ClC 6 H 4 ) in acetonitrile.…”

Reactions of the rhenium fragment (η5-C5Me5)Re(CO)2 with chlorinated ethylenes: Coordination and C–Cl bond activation

“…The lack of reported Re-C(vinyl) bond distances for similar rhenium complexes precludes any comparison with the one found in 3 (2.148 Å ). However, it is quite longer than those reported for Ni(C 2 Cl 3 )(C 6 H 2 Me 3 -2,4,6)(PMe 2 Ph), (1.933 Å ) [10], and Ni(C 2 Cl 3 ) 2 (PMe 2 Ph) 2 , (1.91 Å ) [27] but slightly shorter than those found in complexes containing Re-C(sp 2 ) bonds (cis-Cp * Re(CO) 2 (C 6 HCl 4 )Cl, 2.197 Å [13] and trans-Cp * Re(CO) 2 (C 6 H 2 Cl 2 (MeO))Cl, 2.188 Å [15]). The C@C bond distance of the trichlorovinyl ligand of 1.324 Å shows no unusual features compared with the nickel complexes mentioned above [10,27].…”

“…As a part of our continuing interest in the C-Cl bond activation of chlorinated aromatic molecules by rhenium organometallic complexes of the type Cp * Re(CO) 2 L (Cp * = (g 5 -C 5 Me 5 ), L = CO, N 2 ) [13][14][15][16] in this paper we would like to report the photochemical reaction of the dinitrogen complex Cp * Re(CO) 2 N 2 with PCE and TCE from which the coordination products Cp * Re(CO) 2 (g 2 -chloroethylene) could be isolated and characterized by spectroscopy. Thermal reaction of Cp * Re(CO) 2 (g 2 -C 2 Cl 4 ) in organic solvents, involves an intramolecular C-Cl bond activation to yield the trichlorovinyl complex cis-Cp * Re(-CO) 2 (C 2 Cl 3 )Cl isolated as an analytically and spectroscopically pure sample.…”