Organometallic chemistry alkene/alkyne reactions

Keim W, Behr A, Roper M (1982) Alkene and alkyne oligomerisation, cooligomerisation and telomeiization reactions. In Comprehensive organometallic chemistry, vol 8. Pergamon Press, Oxford... 

Carbozincations constitute undoubtedly one of the most fascinating fields of organozinc chemistry. Whereas alkenes and alkynes are not traditionally considered as electrophiles in polar organometallic chemistry, carbometallation reactions offer many synthetically... 

Grubbs, R. H., Alkene and Alkyne Metathesis Reactions , in Comprehensive Organometallic Chemistry, Pergamon Press, Oxford, 1982, Vol. 8, pp. 499-551. 

A major effort to study the chemistry of the zero oxidation state lanthanides on a preparative scale involved their reactivity with neutral unsaturated hydrocarbons 14, 60). This class of reagents was of interest because reactions of unsaturated hydrocarbons with metals constitute such an important component of organometallic chemistry and because species such as alkenes and alkynes were not common as ligands or reactants in organolanthanide chemistry at that time. 

Review W. Reim, A. Behr, M. Roper, Alkene and alkyne oligomerization, cyclooligomerization and telomerization reactions, in Comprehensive Organometallic Chemistry, (Eds. G. Wilkinson, F. G. A. Stone, E. W. Abel), I rgamon, Oxford, 1984. 

New Applications of TCNE in Organometallic Chemistry, A. J. Fatiadi (1987). Selected reactions used in organometallic synthesis are reviewed. 311 references are given. Structure and bonding of metal-TCNE complexes as well as reactions of TCNE with main-group organometallics, with transition-metal complexes, with metal-coordinated alkenes and alkynes, and reactions of platinum-family complexes are discussed. 

The hydroamination of alkenes and alkynes has been of longstanding interest in organometallic chemistry [26]. Much of the early work in this area focused on early transition metal or lanthanide metal catalyst systems. However, much recent progress has been made in late-metal catalyzed hydroamination chemistry, and several interesting hydroamination reactions that afford nitrogen heterocycles have been developed using palladium catalysts. 

Some general reviews relating to the chemistry of Ru/Os-r hydrocarbon complexes appear in the literature the reactivity of Ru-H bonds with alkenes and alkynes/ aspects of ruthenium/osmium vinylidene/allenylidene/cumul-enylidene complexes,equilibria of M-R/M=CR2/M=CR complexes, the organometallic chemistry of metal porphyrin complexes, and the reactions of [Os(P Pr3)2(CO)HGl], ruthenium pyrazoly I borate complexes,and metallabenzynes. Other reviews relate more to applications of some of the complexes outlined in this chapter. See, for example, metal vinylidenes in catalysis,the development of Grubbs-type alkene metathesis catalysts, applications of ruthenium/osmium carbene complexes in metathesis polymerization, and the role of Ru /V-hetero-cyclic carbene complexes in metathesis polymerization. ... 

Due to the low reactivity of alkyl and arylorganozinc reagents towards alkenes and alkynes, it appears clear that the carbozincation chemistry for this class of reagents is intimately associated with transition metal catalysts. Some of the metal-catalyzed/promoted reactions do indeed produce organozinc reagents as the final organometallic species that can further react with an appropriate electrophile, whereas other processes lead to highly functionalized products by an entirely different pathway. 

Tetrahedrane (11) is the ruthenium analog of the much-studied tricobaltnonacarbonyl clusters Co3(CO)9CR see Cobalt Organometallic Chemistty). The substitution chemistry of (11) has been studied. A starting material is prepared from (11) by reaction with BX3 (equation 2), which gives the chloro and bromo compounds (12). In addition, (11) can also be treated directly with compounds such as diynes to yield interesting substitution products. For example, when (11) is refluxed in THF with diphenylbutadiyne, cis- and trans-alkene isomers of two alkyne insertion regioisomers are formed (equation 3). The product seems to arise from dehydrogenation of one end of the diyne to yield cis and trans enynes and an imsaturated monohydride cluster intermediate, which then reacts with the enynes to yield the allylic derivative products... 

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