Olefin complexes characteristics

As mentioned above, gas-phase coordination of unsaturated C—C bonds to metal cations constitutes another means for double-bond localization. Peake and Gross260 determined the fragmentation of Fe+/olefin complexes by CID spectrometry and reported highly characteristic differences for several constitutional octadiene isomers. High-resolution mass spectrometry proved to be necessary in certain cases due to the isobaric masses of Fe and even two units of C2H4 and/or CO261. Although not based on gas-phase ion/molecule... 

C-E bond formation via hydroalumination, 10, 859 C-E bond formation via hydroboration, 10, 842 olefin cross-metathesis, 11, 195 terminal acetylene silylformylation, 11, 478 Chemspeed automated synthesizer, for high-throughput catalyst preparation, 1, 356 Chini complexes, characteristics, 8, 410 Chiral bisphosphanes, in hydrogenations on DIOP modification, 10, 7... 

Pd and Rh reverse positions below room temperature. The positions of Fe, Co, and Ni relative to these metals is uncertain, but on their general characteristics (6) they would be placed in the neighborhood of Pd and Rh Cu would fall at the end of the sequence. This sequence is quite reminiscent of the coordination strength sequence, particularly in the relative placings of Pt and Ir, followed by Pd and Rh, with Cu at the end. What is however anomalous is the position of the base metal triad in fact, Fe, Co, and Ni are better catalysts for olefin hydrogenation than would be expected on the basis of their ability to form olefin complexes. We will return to this point. 

Formation constants for silver(I)-olefin complexes have been obtained in aqueous solution by potentiometric methods by Hartley and Venanzi 45>. The ligands allylammonium perchlorate, but-2-enyl ammonium perchlorate, allyl alcohol and but-2-en-l-ol, were shown to have affinities for silver(I) comparable with acetate and fluoride ions the complexes are much weaker than the corresponding platinum(II) complexes, possibly due to the non-directional characteristic of the silver component of the a-bond (5s-orbital). The small difference between the formation constants for the allylammonium and but-2-enylammonium complexes and the larger difference between the alcohol complexes was assumed to be an enthalpy effect, arising from an electrostatic repulsion in the case of the unsaturated ammonium cations. 

Anhydrous silver hexafluorophosphate [26042-63-7] AgPF, as well as other silver fluorosalts, is unusual in that it is soluble in ben2ene, toluene, and xylene and forms 1 2 molecular crystalline complexes with these solvents (91). Olefins form complexes with AgPF and this characteristic has been used in the separation of olefins from paraffins (92). AgPF also is used as a catalyst. Lithium hexafluorophosphate [21324-40-3] LiPF, as well as KPF and other PF g salts, is used as electrolytes in lithium anode batteries (qv). 

A number of less hindered monoalkylboranes is available by indirect methods, eg, by treatment of a thexylborane—amine complex with an olefin (69), the reduction of monohalogenoboranes or esters of boronic acids with metal hydrides (70—72), the redistribution of dialkylboranes with borane (64) or the displacement of an alkene from a dialkylborane by the addition of a tertiary amine (73). To avoid redistribution, monoalkylboranes are best used /V situ or freshly prepared. However, they can be stored as monoalkylborohydrides or complexes with tertiary amines. The free monoalkylboranes can be hberated from these derivatives when required (69,74—76). Methylborane, a remarkably unhindered monoalkylborane, exhibits extraordinary hydroboration characteristics. It hydroborates hindered and even unhindered olefins to give sequentially alkylmethyl- and dialkylmethylboranes (77—80). 

Polymer-supported catalysts incorporating organometaUic complexes also behave in much the same way as their soluble analogues (28). Extensive research has been done in attempts to develop supported rhodium complex catalysts for olefin hydroformylation and methanol carbonylation, but the effort has not been commercially successful. The difficulty is that the polymer-supported catalysts are not sufftciendy stable the valuable metal is continuously leached into the product stream (28). Consequendy, the soHd catalysts fail to eliminate the problems of corrosion and catalyst recovery and recycle that are characteristic of solution catalysis. 

The solubihty characteristics of sodium acyl isethionates allow them to be used in synthetic detergent (syndet) bars. Complex blends of an isethionate and various soaps, free fatty acids, and small amounts of other surfactants reportedly are essentially nonirritant skin cleansers (66). As a rule, the more detersive surfactants, for example alkyl sulfates, a-olefin sulfonates, and alkylaryl sulfonates, are used in limited amounts in skin cleansers. Most skin cleansers are compounded to leave an emollient residue on the skin after rinsing with water. Free fatty acids, alkyl betaines, and some compatible cationic or quaternary compounds have been found to be especially useful. A mildly acidic environment on the skin helps control the growth of resident microbial species. Detergent-based skin cleansers can be formulated with abrasives to remove scaly or hard-to-remove materials from the skin. 

Flowever, information concerning the characteristics of these systems under the conditions of a continuous process is still very limited. From a practical point of view, the concept of ionic liquid multiphasic catalysis can be applicable only if the resultant catalytic lifetimes and the elution losses of catalytic components into the organic or extractant layer containing products are within commercially acceptable ranges. To illustrate these points, two examples of applications mn on continuous pilot operation are described (i) biphasic dimerization of olefins catalyzed by nickel complexes in chloroaluminates, and (ii) biphasic alkylation of aromatic hydrocarbons with olefins and light olefin alkylation with isobutane, catalyzed by acidic chloroaluminates. 

This technology has been utilized by BP Chemicals for the production of lubricating oils with well defined characteristics (for example, pour point and viscosity index). It is used in conjunction with a mixture of olefins (i.e., different isomers and different chain length olefins) to produce lubricating oils of higher viscosity than obtainable by conventional catalysis [33]. Unichema Chemie BV have applied these principals to more complex monomers, using them with unsaturated fatty acids to create a mixture of products [34]. 

Heterogeneous Ziegler-Natta catalysts used to polymerize olefins exhibit phenomena characteristic of active site heterogeneity (1- 5). Complex kinetic models which account for this likelihood have been developed and used only in simulation studies (6-7). 

The dihalogen complexes with olefin donors were first identified spectroscopically in the mid-1960s [42-45] and extensive experimental and computational studies have been carried out by Chiappe, Lenoir and coworkers in recent years [46 - 48 ]. These systems are highly unstable, since the complexation of dihalogens with olefins is followed rapidly by the formation of ionic intermediates and further chemical transformations. Therefore, attention in the corresponding work has mostly focused on hindered olefins, although the spectral characteristics of complexes with less sterically crowded and alkyl- as well as chloro-substituted and cyclic olefins are also reported [44]. The absorption maxima for the dihalogen complexes with olefins (evaluated by the subtraction... 

One of the most defining characteristics of the late metal a-diimine polymerization systems is the uniquely branched polyolefins that they afford. This arises from facile p-hydride elimination that late transition metal alkyl complexes undergo. The characteristics of the isomerization process have been the subject of much investigation, particularly with the more easily studied Pd(II) a-diimine system. The process is initiated by P-hydride elimination from the unsaturated alkyl agostic complex 1.17, followed by hydride reinsertion into olefin hydride intermediate 1.18 in a non-regioselective manner (Scheme 5). In doing so, the metal center may migrate... 

The decomposition of aliphatic peroxides produces oxygen radicals too unstable for paramagnetic measurement. These radicals initiate the polymerization of olefins and give the complex mixtures of decomposition products associated with radical mechanisms. On the other hand, aliphatic peroxides are also capable of polar decomposition reactions, a subject to be taken up in Chapter VIII. The characteristic reactions of the less stable oxygen free radicals are /3-cleavage to form... 

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