Group 6 Metal Initiators

Although the tungsten initiators allow a variety of functionalized monomers to be studied, the analogous molybdenum complexes show an even greater tolerance of functional groups.525,526 The synthetic route developed for Mo(NAr)(CHR)(OR )2 allows for a wide variety of imido, alkoxide and alkylidene substituents to be prepared, and several (e.g., (210) and (211)) are commercially available527 530 

The range of functional groups compatible with the molybdenum initiators includes fluoroalk-yls, esters, acetals and maleimides.531,532 However, protic functionalities such as alcohols and acids are not tolerated, and aldehydes terminate the polymerization. 

Confirmation that the polymerizations proceed via metallacyclic intermediates was obtained by studying the ROMP of functionalized 7-oxanorbornadienes. These polymerize slower than their norbornene analogs, allowing NMR identification of the metallacyclobutane resonances and subsequent monitoring of ring opening to the first insertion product. In addition, the X-ray crystallographic structure of complex (212) has been reported.533 

Stereoselective ROMP has been reported with monomer (213). Initiator (211) affords highly stereoregular polymer with 98% trans C=C bonds in the polymer backbone.534 However, when (210) is used, 98% cis-poly-(213) is obtained.535 A similar situation occurs for the diester monomer (214). Furthermore, a rapidly equilibrating mixture of (210) and (211) can be used to allow intermediate cis/trans contents to be manipulated by the stoichiometry of the initiator mixture. 13C NMR536 and dielectric analyses537 suggested that trans-poly-(213) is highly syndio-tactic (92% r dyad content). The ROMP of other fluorinated olefins has been recently reviewed.538 

The molybdenum initiators also allow for functionalization of the polymer end groups. The use of appropriately substituted alkylidene ligands553,554 and functionalized termination agents555 have both been described. A more convenient approach using chain transfer agents has also been developed, initially with substituted cyclopentenes,509 and then with 1,3-dienes and styrenes.556 

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N3-coordinated complexes containing platinum group metal ions have also been synthesized and studied (56,60,61). Steric hindrance has been used to direct binding to N3 in a series of Pd- and Pt-containing complexes of 6,6,9-trimethyladenine (60). Platinum modification was found to have a pronounced effect on the basicity of the adenine moiety. The protonation constants (log Kh values) for the twofold protonation of 6,6,9-trimethyladenine are 4.15 and -0.75, with the initial protonation occurring at N1 followed by N7. The equivalent values for the formation of [Pt(dien)TMA-A3)H]3+ and [Pt(dien)TMA-2V3)H2]4+ are 0.3 and —1.2, respectively. Moreover, the site of initial protonation was found to be N7 (Fig. 19). These observations are supported by theoretical studies (62). 

To summarize briefly, our approach involves initial attack by a relatively nucleophilic metal hydride on coordinated CO. Such reactivity has been demonstrated repeatedly for main-group metal hydrides perhaps the most elegantly worked-out system involves CpRe(C0)2(N0)+ (Cp = Tl-C H ) which, under varying conditions, can be converted to an entire range of products containing CO at different stages of reduction, including formyl, carbene, hydroxymethyl and methyl species (Scheme l). Reactions lead-... 

The concept of using group I metal initiators was applied in order to minimize the toxicity generated by heavy metal residues in the end product PLAs when using metals like aluminum, tin, and lanthanides as initiators. In recent years, dinuclear lithium and macro-aggregates with phenolate ligands have attracted substantial interest, mainly due to uncommon strucmral feamres and their ability to catalyze formation of polyester and various other polymeric materials via ROP [28]. A series of lithium complexes supported with 2, 2-ethylidene-bis (4, 6-di-tert-butylphenol) (EDBP-H2) 2-6, (Scheme 6) are excellent initiators for the ROP of L-lactide in CH2CI2 at 0 °C and 25 °C [33-35]. In this case, the PDIs of the obtained PLAs were quite narrow (1.04—1.14) and a Unear relationship between and the monomer-to-initiator ratio ([M]o/[I]o) existed at 0 °C. Dimeric complexes 4 and 6 were the... 

Titanium alkoxides are also effective and sought-after initiators for the ROP of lactides due to a low toxicity, which minimizes the problems linked to the presence of catalyst residues in commercial PLA products [18, 19]. Despite impressive advancements in the use of Lewis acidic metal initiators in the preparation of PLAs, surprisingly little attention has been paid to the group 4 metal (Ti, Zr, Hf) initiators, probably due to the highly oxophilic nature of M(1V) which has a natural tendency to form aUcoxy-bridged multinuclear complexes. Verkade and coworkers previously demonstrated a series of titanium aUcoxide complexes 118-122 (Fig. 17) that function as moderately efficient initiators in bulk homopolymeization of L-lactide and rac-lactide, some of these initiators displaying a well-controlled polymerization behavior [119]. 

Block copolymers have been successfully synthesized because many metallocene polymerizations of MMA proceed as living polymerizations, and it is possible to have a single one-way crossover from carbanion (alkene) polymerization to MMA (enolate) polymerization with metallocene and related initiators, especially when group 3 transition metal initiators are used [Boffa and Novak, 2000 Desurmont et al., 2000a,b Jin and Chen, 2002 Yasuda et al., 1992],... 

The initial steps are similar to any other mineral extraction process. This involves crushing mineral, froth flotation, gravity concentration and other steps to obtain platinum metal concentrates that may contain about 30 to 40 wt% of platinum group metals. The concentrate is treated with aqua regia to separate soluble metals, gold, platinum, and palladium from other noble metals such as ruthenium, rhodium, iridium, osmium, and silver that remain in... 

Group VIII initiators without metal alkyl co-catalysts Group VIII alkylidenes... 

Percentage composition of C4-products from acetylene hydrogenation over alumina-supported Group VIII metals Initial C2H2/H2 1. 

Hydrosilylations of fluorine-containing alkenes are free radical reactions initiated by UV light or organic peroxides The direction of addition is the same as with fluonnated alkyl halides However, the reaction between hydrosilanes and fluorine-containing olefins catalyzed by platinum group metal complexes may result in bidirectional addition and/or formation of a vinylic silane, the latter by de hydrogenative silylation[/] The natures of both the silane and the catalyst affect the outcome of the reaction[7] A random selection of some typical new reactions of silanes are shown in Table 1 [1, 2, 3 4]... 

In earlier chapters we noted that metal ions could either activate or deactivate an imine with respect to addition of a nucleophile. We will now see an example of metal-ion activation in action. In fact, the complexes that are formed from 6.39 arise as a result of metal-initiated nucleophilic attack at the imine groups. The reaction of the free ligand 6.39 with methanolic cobalt(n) acetate results in the attack of methanol upon one of the imine bonds of the initially formed complex (Fig. 6-39). 

A different type of sequential process is illustrated in entry 18 Os3(CO)i2 behaves as a source of "Os(CO)4 groups, and initial insertion is followed by loss of dihydrogen and metal-metal bond formation. This Os-Os bond is then attacked by further MesSiH (243). 

Studies of the polymerisation of alanine A-carboxylic acid anhydride with diethylzinc or triisobutylaluminium as the catalyst have revealed the relatively fast deprotonation of the monomer NH group by the metal alkyl as the first reaction step. This reaction (easily detectable by evolution of the ethane or isobutane) produces A-metallated initiating species (substituted metal carbamates) which, however, are not monomeric but undergo association via metal-heteroatom coordination bonds [75,175]. 

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