Reference

Reactions of methyl complexes of iron(II) with Lewis bases

Reactions of methyl complexes of iron(II) with Lewis bases. Bellachioma, Gianfranco; Cardaci, Giuseppe; Reichenbach, Gustavo (Dip. Chim., Univ. Perugia, Perugia 06100, Italy). J. Chem. Soc., Dalton Trans., (12), 2593-7 (English) 1983. CODEN: JCDTBI. ISSN: 0300-9246. DOCUMENT TYPE: Journal CA Section: 29 (Organometallic and Organometalloidal Compounds) Section cross-reference(s): 78 Reaction of [MeFe(CO)3(PMe3)2]+ BPh4- with Lewis bases [L; PMe3, PEt3, P(OMe)3, P(OCHMe2)3, p-aminopyridine, MeCN, CO, CH2:CHCN] to give the corresponding [AcFe(CO)2(PMe3)2L]+ BPh4- proceeded via 2 paths. The first involved CO insertion followed by attack by L, and the 2nd involved ligand exchange followed by CO insertion. The relative importance of the paths depended on the nature and concn. of L. Neutral [MeFe(CO2)(PMe3)X] (X = cyano, iodo) also reacted with Lewis bases to give the corresponding [AcFe(CO)(PMe3)2LX] (I). 121-45-9 and 89144-41-2 are just another two chemicals used in this study. I [L = PMe3, P(OMe)3, P(OCHMe2)3, X = iodo] rearranged readily to [MeFe(CO)2(PMe3)L]+ I-. .

Reactivities of activated metal carbonyl clusters

Reactivities of activated metal carbonyl clusters. Ligand substitution kinetics of the ruthenium methoxycarbonyl adduct Ru3(CO)11(CO2CH3)-. Anstock, Martin; Taube, Douglas; Gross, David C.; Ford, Peter C. (Dep. Chem., Univ. California, Santa Barbara, CA 93106, USA). J. Am. Chem. Soc.Several reagents with their cas registry numbers 121-45-9 and 90342-88-4 are used here., 106(12), 3696-7 (English) 1984. CODEN: JACSAT. ISSN: 0002-7863. DOCUMENT TYPE: Journal CA Section: 67 (Catalysis, Reaction Kinetics, and Inorganic Reaction Mechanisms) The stable methoxycarbonyl complex Ru3(CO)11(CO2C3)- formed by the addn. of NaOMe to solns. of Ru3(CO)12 under CO is activated toward ligand substitutions. Comparative rate studies show the methoxycarbonyl group to be ~3 orders of magnitude more labile than Ru3(CO)12 in MeOH solns. Reaction of Ru3(CO)11(CO2CH3)- with P(OCH3)3 gives Ru3(CO)11(P(OCH3)3) as the sole detectable Ru product in 10/90 THF/MeOH solns. but sequential substitution to give Ru3(CO)10(P(OCH3)3)2 is seen in 90/10 THF/MeOH, the reaction pattern differences being the result of the sensitivity of methoxycarbonyl adduct formation consts. to the solvent compn. and to the substituents on the cluster. Kinetic studies suggest a dissocn. pathway to give unsatd. species such as Ru3(CO)10(CO2CH3)- as the predominant mechanism. The increased labilities of the adducts may have particular relevance given the possible roles of methoxycarbonyl complexes in certain homogeneous catalysis cycles. .