A successful synthesis of Cp*Ru(η5-CH2CHCHCHO) (1) was obtained by chromatography on neutral deactivated alumina of Cp*Ru(1−4-η-CH2CHCHCHOSiMe3)Cl (2). The disproportionation reaction of 2 affords compounds 1 and Cp*Ru(1−3-η-endo-syn-CH2CHCHCHO)Cl2 (3). Reaction of compound 1 with diphenylacetylene affords compounds Cp*Ru[1−5-η-syn-CH(Ph)C(Ph)CHCHCH(CHO)] (6), Cp*Ru[1,4,5-η-C(Ph)C(Ph)CH2CHCH2]CO (7), Cp*Ru(1−3-η-CH2CHCHCHO)(η2-PhC⋮CPh) (8), and compounds with cyclic structures, such as Cp*Ru[1,6,7,10,11-η-CH(CH)4CCHC(Ph)CH(CH)2C(O)CH(C6H4)CH(Ph)] (9) and Cp*Ru[3,4,5-η-C(Ph)C(Ph)CHCHCHC(O)](η2-PhCHCHPh) (10). Reaction of compound 3 with diphenylacetylene shows the syn-aldehyde derivative 6, as well as the corresponding kinetic isomer 11, in which the terminal aldehyde group is in anti-position. Treatment of [Cp*RuCl2]2 with CH2CHCHCHOSiMe3 affords compound Cp*Ru[1−3-η-endo-syn-(Me)CHCHCH(OEt)]Cl2 (5). The Ru(IV) complex 5 reacts with diphenylacetylene to give the cyclic 1,2-diphenyl-3-methylcyclopentadienyl complex Cp*Ru[η5-C(Ph)C(Ph)C(Me)CHCH] (12). The investigation of the reactivity of the 2,4-dimethyl-oxopentadienyl of Cp*Ru[η5-CH2C(Me)CHC(Me)O] (4) with excess of diphenylacetylene or dimethyl acetylenedicarboxylate showed the oxopentadienyl/alkyne coupling products Cp*Ru[1−5-η-syn-CH(Ph)C(Ph)CHC(Me)CH(COMe)] (13) and Cp*Ru[1−5-η-syn-CH(COOMe)C(COOMe)CHC(Me)CH(COMe)] (16), along with small amounts of Cp*Ru[1−5-η-syn-CH(Ph)C(Ph)CHC{CH2C(Ph)CH(Ph)}CH(COMe)] (14) and Cp*Ru[1−5-η-syn-CH(COOMe)C(COOMe)CHC{CH2C(COOMe)CH(COOMe)}CH(COMe)] (17), which are products of a second coupling reaction through the activation of one of the C−H bonds of the 2-methyl substituent. Crystallographic studies are reported for compounds 6, 9, 13, 14, and 17. Cp*Ru[1−5-η-CH2C(Me)CHC{CH2C(Me)2CH2C(O)}CH] (18) was also studied in solid state and in solution.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.