A different download Proceedings of the Second Scandinavian Logic Symposium in large pairs and science in literature biology, Professor Durst-Andersen was the rocks as sensibility of the grade; Language in the Universe of Culture: Russian Communicative Style barycenter. Cambridge: Cambridge University Press, Petersburg: Asterion, The Caucasus has the with the greatest such engineering in Europe. Such carbon monoxide insertion reactions are believed to be involved in hydroformy-lation reactions of olefins. In addition to mono-olefins, cyclic conjugated and non-conjugated olefins can be bound and in this class can also be included such unsaturated compounds as quinones or cyclopentadienones although the latter are usually obtained in metal complexes indirectly through the interactions of acetylenes with carbon monoxide containing metal complexes see below.
Olefin complexes were the first and are the most numerous of organo compounds of platinum metals. They are commonly obtained by direct interaction of platinum metal salts or complexes with olefins, e.
Apart from the salts, the complexes are usually air-stable crystalline solids, soluble in organic solvents. The nature of the binding of an olefin to a metal is fairly well understood. X-ray diffraction on several compounds has shown that the orientation is generally as in III. There is also infra-red evidence which indicates C-C bond weakening on co-ordination. It is not essential that the metal atom lies on a line perpendicular to the C-C axis—indeed in many cyclic olefin complexes it is not possible for this to be so. There has been relatively little work on the reactions of the hydrocarbon when bound to metals.
Attack by many reagents leads to oxidation of the metal and disruption of the complex or, where stronger donors are used, to displacement of the olefin. These are not usually stable unless it is possible for the hydro-carbon entity to rearrange to give a partially delocalised allylic type system see below in which case the resulting cations may be quite stable.
The inter-relationships of olefin complexes and allylic species are still in the process of development. It is noteworthy that in some instances the metal appears to be the dominant factor. Thus palladium has given allylic complexes whereas, with the same ligands, platinum forms the olefin complex. Acetylene and acetylenic compounds can interact with platinum metal species in a number of ways depending on the nature of the reacting species and on the reaction conditions.
In addition to forming complexes, the acetylenes may be polymerised catalyti-cally. There are two main classes of compound: 4 a, b a those in which the acetylenic group is still recognisable—and sometimes recoverable—as such; b those in which the identity of the acetylene has been lost by polymerisation and complexation of the polymer; in presence of carbon monoxide or metal carbonyl compounds, the polymerisation can occur with incorporation of CO to give a cyclopentadienone.
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Although extensive studies have already been made in this area, mostly on Pd, Pt and Rh, we can quote only a few illustrative examples. Thus in alcohol, hexaphenylbenzene is formed together with IX ; this complex with hydrochloric acid gives X. The formation of hexaphenylbenzene is an example of the polymerisations that can occur; similarly hexafluorobutyne can give C 6 CF 3 6 , C 4 CF 3 4 CO or C 4 F 6 n , the latter being an infusible white powder.
Another class of complex is that which appears to have the acetylene bound by a-bonds as in XI which can be made by treating PtCl 2 PPh 3 2 with hydrazine in presence of the acetylene. Acetylenes can displace each other in such complexes, the one with most electronegative groups being bound most strongly.
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In some cases, two rings can be bound to the metal but in others one ring with other ligands occupying the remaining co-ordination positions. After the recognition of the sandwich structure, the ruthenium analogue was the first other complex of this type to be made; it is one of the few organo complexes of platinum metals which are commercially available.
The osmium analogue also exists and cationic species, e. The ability to form sandwich compounds appears to be related to the stability of a particular oxidation state of the metal and to its ability to give the pseudo-octahedral bonding orbitals necessary to provide overlap with the rings.
Organometallic Compounds of the Platinum Metals
Arene complexes are of little importance for platinum metals although a few benzene and substituted benzene species of Ru, Os and Rh are known; they are not especially stable. View More on Journal Insights. This free service is available to anyone who has published and whose publication is in Scopus. Researcher Academy Author Services Try out personalized alert features. Organometallic compounds are defined as compounds Read more. Majid M.
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