Thiolates lanthanide

LnibtsahiSR). Complex [Gd(btsa)2(/i-StBu)]2 has been the first structurally characterized lanthanide thiolate complex (Gd-S, 2.760(5), 2.823(5) A) and was... 

A number of lanthanide thiolates have been synthesized in recent years and are discussed in Section 4.4.3. 

Thiolates and Related Systems. Lanthanide thiolates have only been characterized in detail recently. Monomeric species have been obtained using bulky Ugands, such as the three-coordinate (pyramidal) Sm(SC6H2-t-Bu-2,4,6)3 (Figure 19) ... 

Bis(indenyl)lanthanide thiolate complexes of the type (C9pl7)2LnSR(THF) are formed in the reaction of tris(in-denyl) lanthanide with equimolar amounts of thiols (Scheme 182). The complexes were characterized by elemental... 

Quite a number of asymmetric thiol conjugate addition reactions are known [84], but previous examples of enantioselective thiol conjugate additions were based on the activation of thiol nucleophiles by use of chiral base catalysts such as amino alcohols [85], the lithium thiolate complex of amino bisether [86], and a lanthanide tris(binaphthoxide) [87]. No examples have been reported for the enantioselective thiol conjugate additions through the activation of acceptors by the aid of chiral Lewis acid catalysts. We therefore focussed on the potential of J ,J -DBFOX/ Ph aqua complex catalysts as highly tolerant chiral Lewis acid catalyst in thiol conjugate addition reactions. 

Many other lanthanide-based initiators have been shown to polymerize MMA, including lanthanocene amides,464 168 alkoxides,469 substituted indenyl and fluorenyl bivalent ytterbocenes,470,471 hexamethylphosphoric triamide thiolates,472 and allyl, azaallyl, and diazapentadienyl complexes.473... 

The aim of this chapter is to review the chemistry of chalcogenolates in the last 10 years. The more recent reviews in this field included chalcogenolates of the s-block elements,13,14 early transition metal thiolates,15 metal complexes with selenolate and tellurolate ligands,16 copper(I), lithium and magnesium thiolates,17 functionalized thiolate complexes,18 19 pentafluorobenzenethiolate platinum group compounds,20 tellurium derivatives,21 luminescent gold compounds,22 and complexes with lanthanide or actinide.23... 

Cf produces two fission products that travel in opposite directions. If one projectile hits the sample, ions will be produced. These ions may then be focused and measured by TOF MS. The other projectile may be used to measure the start of the ionization process. This method has been used to study the ions produced from the ionization of metal complexes such as cadmium thiolates (33) and lanthanide phthalocyanine complexes (34). This method has also been used on metal oxides such as La203 to produce metal oxide cluster ions (35). 

Metals. Lanthanide metals are also considered as valuable precursors. For example, alkoxides derived from cheap and low-boiling-point alcohols have been alternatively synthesized from metals in the presence of HgQ2 as catalyst [133]. Representative and specific methods of preparation include transmetalla-tion reactions (Eq. 7-9) [134], using ammonia solutions of ytterbium and europium as synthetic reagents (Eq. 10) [135] and the generation of thiolate complexes from disulfides (Eq. 11) [136],... 

Much of this work has been directed towards materials-based applications, as volatile compounds might be CVD precursors see Chemical Vapor Deposition) and the ability of the thiolates and their fellows to react with the free chalcogens may assist doping lanthanide ions into optical and electrical materials. Thus, thermolysis of the [Ln(SePh)3(thf)3] (Ln =... 

Interestingly, four examples exist of mixed-metal thiolate complexes in which one or more lithium thiolate moieties are present within an aggregate that also contains a lanthanide or actinide metal thiolate unit (Table XIV). These species... 

Metal thiolate complexes will reduce elemental sulfur or red selenium via the oxidative elimination of RSSR. In a similar manner, metal selenolate complexes ean be used to reduce elemental selenium. The resulting E ligands favor the formation of polynuclear cluster complexes, due to the greater tendency of E (vs. RE ) to form bridging interactions between metal centers. Originally developed in the synthesis of [Fe4Se4(SPh)4], this method has been well utilized in the synthesis of a number of iron thiolate/sulfide clusters, as well as their selenide counterparts (Equation (5)). More recently, sulfur- and selenium-containing lanthanide clusters (see Section 7.2.5.5) have been synthesized by the displacement of ER from Ln(ER)3 ... 

These intramolecular hydroaminations lead to the formation of chiral products. Thus, several studies have been devoted to developing ligands for enantioselective, intramolecular hydroaminations of olefins catalyzed by lanthanide complexes. ° Selectivities of these reactions with chiral cyclopentadienyl derivatives have been modest. Selectivities have been higher with catalysts containing non-cyclopentadienyl ligands. Some of tlie most selective catalysts are the yttrium complexes of the bis(thiolate) ligands reported by Livinghouse, the scandium and lutetium complexes of 33 -disubstituted binaphtholates reported by Hultzsch, and the BINAM-based bisamidates of Schafer.- A representative cyclization catalyzed by a member of each of these classes of catalyst are shown in Equation 16.64. 

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