Catalysts lanthanide coordination type

Lanthanide-based catalysts, despite finding a lot of application in homogeneous catalysis, can be rather problematic due to the lability of some ligand types and the versatility of their coordination chemistry in the -1-3 oxidation state this makes the controlled synthesis of single-site Ln complexes a quite ambitious goal [92]. McLain and coworkers first demonstrated the high potential of a homoleptic yttrium complex Y(OCH2CH2NMe2)3 as ROP catalyst for the preparation of PLA from rac-lactide and that it promotes a rapid and controlled polymerization... 

The first report on the coordination polymerisation of epoxide, leading to a stereoregular (isotactic) polymer, concerned the polymerisation of propylene oxide in the presence of a ferric chloride-propylene oxide catalyst the respective patent appeared in 1955 [13]. In this catalyst, which is referred to as the Pruitt Baggett adduct of the general formula Cl(C3H60)vFe(Cl)(0C3H6),CI, two substituents of the alcoholate type formed by the addition of propylene oxide to Fe Cl bonds and one chlorine atom at the iron atom are present [14]. A few years later, various types of catalyst effective for stereoselective polymerisation of propylene oxide were found and developed aluminium isopropoxide-zinc chloride [15], dialkylzinc-water [16], dialkylzinc alcohol [16], trialkylalumi-nium water [17] and trialkylaluminium-water acetylacetone [18] and trialkyla-luminium lanthanide triacetylacetonate H20 [19]. Other important catalysts for the stereoselective polymerisation of propylene oxide, such as bimetallic /1-oxoalkoxides of the [(R0)2A10]2Zn type, were obtained by condensation of zinc acetate with aluminium isopropoxide in a 1 2 molar ratio of reactants [20-22]. 

The d-f heteronuclear or lanthanide-transition metal (abbreviated as Ln-M) complexes attract interest from both academic and industry because of the challenge for their synthesis, the novelty of their structures, and their potential application as advanced materials, such as molecular or nano magnets,bimetallic catalysts, and sensors. The complexes can be assigned to three categories based on the nature of the Ln-M interaction (a) complexes with direct Ln-M bonding, (b) complexes with Ln-M interactions bridged by ligands, and (c) the complexes with ionically associated Ln-coordination units and M-coordination units. Most of the d-f heteronuclear complexes of carboxylic acids reported so far are found with type (b) structure, and very few of them are of structure type (c). The lanthanides and the transition metals in these complexes are far away from each other, and no direct Ln-M interactions have been observed. 

The dissociation of the dimer [Cp 2Y(/i-H)]2 to the Cp 2YH monomer is an important process in the reactions of the dimer with alkenes. The kinetics and formation of yttrium alkyl complexes from [Cp 2Y(//-I I)]2 and alkenes have been investigated.587 In situ prepared dimeric bis(pentamethylcyclopentadienyl)yttrium hydride reacted rapidly with 3,3-dimethyl-l,4-pentadiene in methylcylohexane-r/ at — 78 °C and formed a bright yellow solution of the t/°-yttrium(m)pentenyl chelate complex Cp 2Y[7/,7/2-CI I2CI I2CMc2CI I=CH2] in 98% yield (Scheme 130). This pentenyl chelate complex was also prepared in toluene-// in 84% yield. The chelate complex was stable for about 2 weeks at — 78 °C but decomposed after a few hours at —50 °C. The complex was characterized without isolation by 1H and 13C NMR spectroscopy at —100 °C such complexes can be regarded as models for the coordination of alkenes to lanthanide and isoelectronic grouop 4 polymerization catalysts.588 Agostic interactions in yttrium alkyls of the type... 

The discovery of Ziegler-Natta catalysts led to many industrial and academic investigations on other kinds of metallic complexes for polymerization of different monomers. Several organometallic and coordination compounds have been synthesized and probed as catalytic systems. They have been classified based on generations or groups, transition-metal type, the chemical structure, the type of activator, and their applications in polymerization processes [2]. Currently, there are different groups of initiator systems based on early and late transition metals or lanthanide complexes, which have been studied in polymerization catalysis [3]. 

This type of epoxidation is proposed to proceed via formation of a lanthanide peroxide (4.86) that coordinates to the carbonyl group and undergoes 1,4-addition to give an enolate (4.87) (Figure 4.6). Cyclisation of the enolate forms the epoxide product and regenerates the catalyst. 

We started our research efforts to develop a new type of Lewis acid that could be used in aqueous media. The chemistry of metal trifluoromethanesul-fonates (triflates) [2], some of which have been used as Lewis acids, has been studied in our laboratories [3]. One of the most successful examples is the use of chiral diamine-coordinated tin(ll) triflate as a chiral Lewis-acid catalyst in asymmetric aldol and related reactions [3c-e]. Metal triflates have several unique properties compared with the corresponding metal halides, and, in the course of our investigations to search for other metal triflates, we first focused on lanthanide triflates [4]. 

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