Search

Irradiation (λmax = 300−375 nm) of FvRu2(CO)4 (1, Fv = η5:η5-bicyclopentadienyl) or (μ2-η1:η5-cyclopentadienyl)2Ru2(CO)4 (2) with dimethyl cis- or trans-butenedioate resulted in FvRu2(η2-trans-CHRCHR)(CO)3 (3, R = CO2CH3). Prolonged irradiation of 1−3 provided FvRu2(η2-trans-CHRCHR)2(CO)2 (4a, R = CO2CH3) and FvRu2(η2-cis-CHRCHR)(η2-trans-CHRCHR)(CO)2 (4b, R = CO2CH3). Photocatalytic isomerization of cis to trans alkene occurred in the presence of 1−4. Irradiation of 1−3 with dimethyl butynedioate produced FvRu2(μ2-η2-dimethyl butynedioate)(CO)3 (5). Prolonged irradiation of 1−5 with the alkyne afforded FvRu2(μ2-η2:η4-CRCRCRCR)2(CO) (6, R = CO2CH3). Irradiation of a THF solution of 6 generated FvRu2(μ2-η2:η4-CRCRCRCR)2(THF) (7, R = CO2CH3). Photochemical alkyne cyclotrimerization was observed in the presence of 1−7. In the presence of CO, 7 reverted to 6 thermally. Heating 7 in the presence of dimethyl cis-butenedioate, thiophene, PPh3, or dimethyl sulfoxide (DMSO) afforded FvRu2(μ2-η2:η4-CRCRCRCR)2(L) (8...

(Fulvalene)hexacarbonyldirhenium (1) furnishes the first silylene fulvalenedimetal complex 3 by double Si−H activation. The solid-state structure of the molecule was determined by X-ray analysis and its solution dynamics by 1H NMR spectroscopy.

The electron-reservoir complexes [FeICp(C6H6)], [FeICp(C6Me6)], and [FeICp*(C6Me6)] (Cp = η5-C5H5; Cp* = η5-C5Me5) have been used as initiators in THF for the electron-transfer-chain-catalyzed (electrocatalyzed) synthesis of the homobimetallic zwitterions [(CO)3M-FvM+(CO)2(PR3)2] (M = Mo, W; Fv = μ2-η10-fulvalene; R = Me, OMe) from [M2Fv(CO)6] and PR3 and of the heterobimetallic zwitterions [(CO)3MIFvM2(CO)(PR3)2] (M1 = Mo, W; M2 = Fe, Ru) from [M1M2Fv(CO)5] and PR3. Cyclic voltammetry (CV) experiments (DMF, 0.1 M n-Bu4NBF4, Pt, 0.400 V s-1) show that the CV's of the homobimetallic starting materials are unchanged in the presence of PR3 (R = Me, OMe) whereas those of the heterobimetallic complexes in the presence of PMe3 show only the CV's of the zwitterions. This indicates that the electrocatalytic process of the homobimetallic complexes is slow on the electrochemical time scale whereas that of the heterobimetallic complexes with PMe3 is fast on the same time scale. This dichotomy is taken into account i...

Preparation de (η 5 :η 5 -C 10 H 8 )(CO) 4 Co 2 , (η 5 :η 5 -C 10 H 8 )(CO) 4 Ru 2 et (η 5 :η 5 -C 10 H 8 (CO) 6 M 2 (M=Cr, Mo, W)

L'etude par diffraction RX du compose Cp 2 Co 2 [CSi(CH 3 ) 3 ] 2 montre la presence d'une double liaison Co−Co. Conversion sequentielle d'un precurseur mononucleaire en complexe alkyne mono-di- et trinucleaire. Spectre RMN

Etude RX de la structure cristalline de [Fv Mo 2 (CO) 6 ], et etude de son traitement thermique, photolytique et chimique

Le (η 5 :η 5 -fulvalene)-Mo 2 (CO) 6 est dialkyle par le diiodo-1,3 propane pour donner un oxa-1 cyclapentylidene-2 fulvalene-Mo 2 (CO) 5 . Etude de degradation thermique et photochimique