Metal aryloxides coordination

The metals thorium and uranium (as with the chemistry in general of these elements) dominate actinide aryloxide chemistry. Synthetic strategies normally focus on the halides reacting with group 1 metal aryloxides or reaction of metal amides with phenols. An important piece of early work was the demonstrated interconversion of eight-coordinate [UMe4(dmpe)2] and [M(OPh)4(dmpe)2] (M = Th, U Table 6.20) by addition of phenol or MeLi to each substrate respectively. The reaction of the cyclometallated... 

Aryloxide coordination compounds of Co(n) and Co(m) typically adopt octahedral geometries (Table 6.36). In a number of these derivatives the metal coordination sphere is completed by chelation of orfAo-substituents on the aryloxide, e.g. in [Co(OC6H2Cl3-2,4,6)21-2] (L = imidazole, L2 = TMEDA) compounds where Co-Cl interactions are present." " The complex [Co(OPh)(PPh3)3]" is tetrahedral while treatment of... 

The stereochemistry of Mg and the heavier alkaline earth metals is more flexible than that of Be and, in addition to occasional compounds which feature low coordination numbers (2, 3 and 4), there are many examples of 6, 8 and 12 coordination, some with 7, 9 or 10 coordination, and even some with coordination numbers as high as 22 or 24, as in SrCdn, BaCdn and (Ca, Sr or Ba)Zni3. " Strontium is 5-coordinate on the hemisolvate [Sr(OC6H2Bu3)2(thf)3]. jthf which features a distorted trigonal bipyramidal structure with the two aryloxides in equatorial positions. ... 

The alkoxides and aryloxides, particularly of yttrium have excited recent interest. This is because of their potential use in the production of electronic and ceramic materials,in particular high temperature superconductors, by the deposition of pure oxides (metallo-organic chemical vapour deposition, MOCVD). They are moisture sensitive but mostly polymeric and involatile and so attempts have been made to inhibit polymerization and produce the required volatility by using bulky alkoxide ligands. M(OR)3, R = 2,6-di-terr-butyl-4-methylphenoxide, are indeed 3-coordinate (pyramidal) monomers but still not sufficiently volatile. More success has been achieved with fluorinated alkoxides, prepared by reacting the parent alcohols with the metal tris-(bis-trimethylsilylamides) ... 

Metal-Oxygen Bond Lengths, M—O—C Angles, and Torsion Angles for Three-Coordinate Aluminum and Gallium Alkoxides and Aryloxides... 

Overall, the alkali metal alkoxide and aryloxide systems are excellent examples in demonstrating the effects of steric influences on both molecular aggregation and also on the nature of any extended network architecture adopted. The large database of O-M complexes that have now been identified has led to a good deal of predictability regarding the coordination chemistry of these species. 

Table 1. Monomeric A1R1R2R3 complexes incorporating simple, monodeprotonated aryloxide ligands (Rl) and, where appropriate, Lewis base (L). R2, R3 = other ligands, C.N. = coordination number of the metal... 

In the context of bidentate ligands, and in a similar vein to the polyfunctional aryloxides discussed above [141, 142, 146, 147], the chelation of a metal centre by deprotonated j5-diketones is a recurrent feature of monomeric organooxide complexes of aluminium. The employment of such ligands results in the observation of simple hexa-coordinate complexes which incorporate three [RC(0)C(H)C(0)R ] moieties (R = R = Me [177,178], CF3 [179], Ph [180, 181] R = f-Bu, R = CF3 [182]). More recently, the cocrystallisation of M(acac)3 (M = Al, Cr) has allowed the crystallographic study of metal disorder in a series of solid solutions of stoichiometry Ali, cCi x(acac)3 (x = 0.02-0.91) [183, 184]. Chelation of the metal centre similar to that reported in monomeric ] -diketonates has also been noted in the presence of... 

A hither facet of research has involved the structural characterisation of aluminium complexes which incorporate polydentate salen-type ligands. These have been noted in both neutral and monocationic (ion-separated) contexts (the latter requiring that the metal centre be stabilised by an external Lewis base) [35]. While such charged systems are invariably mononuclear the same is only usually true of their neutral analogues by virtue of the sterically demanding bis(aryloxide), chelating ligand. In the context of these latter complexes, dimerisation has been noted [251] while, more recently, the employment of flexible alkyl chains between two salen-coordinated aluminium ions has enabled the observation of dinuclear compounds [160, 161]. 

REACTIONS OF METAL ALKOXIDES AND ARYLOXIDES 15.3.5.1 Ligand Coordination... 

The coordination of an alkoxide or aryloxide can lead to a mixed metal derivative.149 In some cases, ligand exchange can take place to generate a neutral adduct (equation 55).IS4... 

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