Complexity of ligands

In 1965, Breslow and Chipman discovered that zinc or nickel ion complexes of (E)-2-pyridinecarbaldehyde oxime (5) are remarkably active catalyst for the hydrolysis of 8-acetoxyquinoline 5-sulfonate l2). Some years later, Sigman and Jorgensen showed that the zinc ion complex of N-(2-hydroxyethyl)ethylenediamine (3) is very active in the transesterification from p-nitrophenyl picolinate (7)13). In the latter case, noteworthy is a change of the reaction mode at the aminolysis in the absence of zinc ion to the alcoholysis in the presence of zinc ion. Thus, the zinc ion in the complex greatly enhances the nucleophilic activity of the hydroxy group of 3. In search for more powerful complexes for the release of p-nitrophenol from 7, we examined the activities of the metal ion complexes of ligand 2-72 14,15). 

Like the ammines, rhodium complexes of ligands like bipy and phen have a significant photochemistry. Therefore, on irradiation, solutions of cw-[Rh(L-L)2X(H20)]2+ (X = halogen) gradually convert to c/s-[Rh(L-L)2X(H20)]2+, though much more slowly than with the ammines [101]. 

Nickel(II) complexes of ligands 38 (R=H,Me R =H,Me,Et,Tr,CH30 R =H, CH3O R =H, F, CH3O) are highly active catalysts for ethylene polymerization [86,159], whereas palladium(II) complexes possess catalytic properties in the copolymerization of CO and alkenes [160] (Scheme 36). 

The first examples of cationic exchange of bis(oxazoline)-metal complexes used clays as supports [49,50]. Cu(II) complexes of ligands ent-6a, 6b, and 6c (Fig. 15) were supported on three different clays laponite (a synthetic clay), bentonite, and montmorillonite KIO. The influence of the copper salt from which the initial complexes were prepared, as well as that of the solvent used in the cationic exchange, was analyzed. 

Carbonyl- and imino-ene reactions were also catalyzed by the bis(oxazo-line)-copper complexes of ligands 6a, 6b and 11b supported on zeoHte Y (Scheme 13) [69]. The enantioselectivities obtained with the supported catalysts were similar or better than those obtained in homogeneous phase with the same ligands. Some relevant examples are shown in Table 12. 

Metal complexes of ligands containing a sulfur donor in conjunction with nitrogen, oxygen or a second sulfur have been reviewed in the past [11-13]. For example, reviews of the coordination compounds of dithiophosphates [14], dithiocarbamates [15, 16], dithiolates [17], dithiodiketonates [18], and xanthates [16] have appeared. The analytical aspects [19] and the spectral and structural information of transition metal complexes of thiosemicarbazones [20, 21] have been reviewed previously. Recent developments in the structural nature of metal complexes of 2-heterocyclic thiosemicarbazones and S-alkyldithiocarbazates, depicted below, are correlated to their biological activities. 

Lippard characterized the structural effect of variation in the alkyl bridge length in tropocoro-nand complexes of zinc (80). Six complexes of ligands with bridge lengths from n = m = 3 to n = m = 6 were structurally characterized.702 The complexes had distorted tetrahedral-square planar geometries, with the exception of the m = n = 3 adduct which was five-coordinate with an additional pyridine ligand. 

Dendrimers built around a metal complex as a core. These compounds can be considered metal complexes of ligands carrying dendritic substituents (Fig. 1 a). The most commonly used metal complex cores are porphyrin complexes, polypyridine complexes, and ferrocene-type compounds. 

It is well known that, when treated with complex substrates, cyclopenta-diene can form complexes with cyclopentadiene, cyclopentadienyl, and even cyclopentenyl ligands. The same possibilities are found for bora-2,5-cyclohexadienes, but with the additional complexity of ligand isomerism. 

In the present account, the standard preparations and analytical procedures employed for certain groups of compounds are not recapitulated. The reader is rather directed to the more special properties of the complexes. Many of the simple compounds of isocyanides RNC with R = Me, Et, nPro, iPro, Ph, etc. were published in the early literature.2,3,5 Almost all of the later work is dedicated to complexes of ligands with R groups of a specific shape or functionality which allow an influence on the molecular properties or the association modes. 

Condensation of 2,6-diacetylpyridine with bis(3-aminopropane)amine in the presence of small ions such as Mn(n), Co(n), Ni(n) or Cu(n) readily leads to formation of the corresponding monomeric (14-membered) macrocyclic complexes of ligand (83). However, when the large Ag(i) ion is used as the template, then a dimetallic complex of a 28-membered macrocycle of type (88) is produced. This example illustrates well the importance of metal-ion size in promoting template reactions. 

While Josiphos 41 also possessed an element of atom-centered chirality in the side chain, Reetz reported a new class of ferrocene-derived diphosphines which had planar chirality only ligands 42 and 43, which have C2- and C -symmetry, respectively.87 Rhodium(i)-complexes of ligands (—)-42 and (—)-43 were used in situ as catalysts (0.75 mol%) for the hydroboration of styrene with catecholborane 1 for 12 h in toluene at — 50 °C. The rhodium/ i-symmetric (—)-43 catalyst system was the more enantioselective of the two - ( -l-phenylethanol was afforded with 52% and 77% ee with diphosphines (—)-42 and (—)-43, respectively. In both cases, the regioselectivity was excellent (>99 1). With the same reaction time but using DME as solvent at lower temperature (—60 °C), the rhodium complex of 43 afforded the alcohol product with an optimum 84% ee. 

A few linear tetranuclear complexes of ligands related to dpa have been structurally characterised, namely [Ni4(phdpda)4] (phdpda = dianion of A-phenyldipyridylamine),39 [Cu4(dphip)4]2 + (dphip = anion of 2,6-bis(phenylamino)piperidine),37b and [Cr4(dpf)4Cl2]2+ (dpf = anion of bis(2-pyridyl)formamidine),38 but no pertinent electrochemical investigation is available. 

The dissociation rate constant is now composite, = k ik 2/k2- Following the first bond rupture (k 2) the competition between further bond rupture (/ , ) and reformation (Atj) which may lead to a small k j/k2 is the basic reason for the high kinetic stability of the chelate. The problem of complete dissociation is intensified when complexes of ligands of higher dentate character are examined. The situation is altered when the successively released donor atom(s) can be prevented from reattachment (see subject of accelerated substitution). 

Application of the coupling reactions described in the previous section has given many organometallic complexes of ligands containing diyne fragments, which may not be directly coordinated to a metal center. The following surveys this area briefly and describes some recent applications of these systems in the construction of novel molecular architectures. 

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