Advances in Organometallic Chemistry, Vol. 37 by F. Gordon (ed.), A. Stone (ed.), Robert West (ed.)

By F. Gordon (ed.), A. Stone (ed.), Robert West (ed.)

This greatly acclaimed serial includes authoritative experiences that tackle all points of organometallic chemistry, a box which has improved significantly because the booklet of quantity 1 in 1964. just about all branchesof chemistry now interface with organometallic chemistry-the research of compounds containing carbon-metal bonds. Organometallic compounds diversity from species that are so reactive that they simply have a brief lifestyles at ambient temperatures to species that are thermally very sturdy. Organometallics are used largely within the synthesis of valuable compounds on either huge and small scales. commercial approaches regarding plastics, polymers, digital fabrics, and prescription drugs all depend upon developments in organometallic chemistry. Key gains* In simple study, organometallics have contributed inter alia to:* steel cluster chemistry* floor chemistry* The stabilization of hugely reactive species by means of steel coordination* Chiral synthesis* The formula of a number of bonds among carbon and the opposite components and among the weather themselves

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R . R . : Gallaher, K. ; Wang, Y. C . ; Bauer, S . H. unpublished results cited in J . Am. Chem. Soc. 1974, 96, 17. (44) Karl, R. R . ; Wang, Y. ; Bauer, S. H. J . M o l . Strrrct. 1975, 25, 17. : Sakurai, H. unpublished results. (46) Gleiter, R . ; Schafer, W. Ace. Chem. Res. 1990,23, 369. (47) Maier, G. Angew. Chem. Itit. Ed. Engl. 1988, 27, 309. (48) Jarrold, M. F. P. Angew. Chem. I n t . Ed. Engl. 1992,31, 172; Zybill, C. Angew. Chem. Int. Ed. Engl. 1992,31, 173. ; Curl, R. ; Tittel, F. K .

RU+> C Me3P\" ~ cac - R \ CI R 28 isolated for R = Ph only CI HC=CCR20H. 24 hr , I Ru+ =C,' CI 27 SCHEME 7 OMe R R 51 Transition Metal Allenyl Complexes Dixneuf and co-workers have performed detailed investigations into the analogous chemistry of the isoelectronic derivative [RuC12(q6-arene)(PR3)] (21c-e), and they revealed that by varying both the electronic and steric properties of the metal fragment markedly different reactivities from those observed by Selegue could be achieved. The less electron-rich [RuC12(q6-C6Me6)(PMe3)] was reported to react with HC=CCR20H (R # H) and NaPF, in methanol to give the vinylcarbene complex [RuCI(qhChMe6)(PMe3){q'-C(OMe)CH=CR2}]-' (27) ( 2 1 ~ )Shorter .

2). The lowest energy absorption band is forbidden when the cubane has high symmetry but can be weakly allowed when it has low symmetry. Semiempirical CNDO/S calculation shows that the spectrum shape in the low energy region depends strongly on substituents (39). 0 5 . 0 20 0 m 254 300 350 400 450 so0 AIm FIG. 9. Electronic absorption spectra of cubanes 17, 19, and 20 in hexane. butyl; trimethylsilyl-, and phenyl-substituted octasilacubanes, tert-butylsubstituted cubane 17 has the lowest energy absorption band.

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