Coordination chemistry ligand complexes

The chemistry of zinc ammine complexes is well known. There are X-ray structural examples of both the tetrahedral tetra-ammine and octahedral hexa-ammine.90,91 Four- and five-coordinate mixed ligand complexes are common and participation in coordination networks as terminal ligands is observed.92,93... 

To examine the chemical behavior of these new ligands 48-50 in coordination chemistry, tricarbonyl complexes with manganese and rhenium were synthesized from [MnBr(CO)s] and [ReBrCCOls] as described earlier for the other heteroscorpionate ligands (Scheme 28). The purpose of these tricarbonyl complexes was to verify tripodal binding of the solid-bound ligand. The protected OH linker in 50 acts as model for the solid phase bound ligand. 

The halide ligands, and particularly those of chloride, are the most propagated ones in modern coordination chemistry. Their complex compounds are represented in classic [89-91] and modern editions [1, vol. 2 3-5,32,73,92]. Coordination compounds of practically all metals and halogens have been synthesized and characterized. Presentation of the enormous amount of material available for the complexes of this type is beyond the limits of the present book. 

Bidentate ligands such as diamines and diphosphines occupy a special position in coordination chemistry, providing complexes that have well-defined geometries and low CNs as a result of chelation. Furthermore, these complexes are favored entropically and hence are less labile than their bis(monodenate) ligand counterparts. Consequently, there have been numerous studies to incorporate sterically and electronically unusual phosphole fragments into bidentate ligand frameworks. 

The reaction of carbonyl sulfide with [M(02)(PPh3)2] (where M = Pd or Pt) has resulted in the first reported examples of transition metal complexes of the monothiocarbonate anion (47 R = 0 ). Bidentate S—O coordination was concluded from P H NMR analyses of these compounds. A short structural review of metal complexes of monothiocarbamate ions (47 R = N(R )R") demonstrates their varied coordination chemistry. In complexes of the dialkyl forms the sulfur atom is seen to have considerable mercaptide character , whereas aromatic amine derivatives demonstrate C—S and M—S partial multiple bonding.A review on the coordination chemistry of these ligands has appeared. Additional detail is provided in Chapter 16.4 of this volume. 

A deactivating agent for copper-activated sphalerite is any species that has sufficient affinity for copper(I) or (II) to compete for it with sulfide ions in the surface lattice of the mineral, thus removing it from the surface. Ligands such as cyanide or ethylenediamine, which coordinate strongly to copper, have therefore been found to be the most effective. A knowledge of the stability of the species present in a system composed of H+, Zn +, Cu +, and CN ions has enabled the extent of deactivation Ijy cyanide ion to be predicted the results of these predictions are compared with experimental observations in Figure 2. This approach has been successfully extended to the effects of pH and the presence of other ions such as carbonate on the activation and deactivation processes, and is a pertinent example of the quantitative application of coordination chemistry to complex systems. 

Lanthanide Complexes with Multidentate Ligands Lanthanide Oxide/Hydroxide Complexes Lanthanides Coordination Chemistry Solvento Complexes of the Lanthanide Ions Trivalent Chemistry Cyclopentadienyl. 

The majority of U(V1) coordination chemistry has been explored with the trans-ddo s.o uranyl cation, UO " 2- The simplest complexes are ammonia adducts, of importance because of the ease of their synthesis and their versatihty as starting materials for other complexes. In addition to ammonia, many of the ligand types mentioned ia the iatroduction have been complexed with U(V1) and usually have coordination numbers of either 6 or 8. As a result of these coordination environments a majority of the complexes have an octahedral or hexagonal bipyramidal coordination environment. Examples iuclude U02X2L (X = hahde, OR, NO3, RCO2, L = NH3, primary, secondary, and tertiary amines, py n = 2-4), U02(N03)2L (L = en, diamiaobenzene n = 1, 2). The use of thiocyanates has lead to the isolation of typically 6 or 8 coordinate neutral and anionic species, ie, [U02(NCS)J j)/H20 (x = 2-5). 

The chemistry of Cr(III) in aqueous solution is coordination chemistry (see Coordination compounds). It is dominated by the formation of kineticaHy inert, octahedral complexes. The bonding can be described by Ss]] hybridization, and HteraHy thousands of complexes have been prepared. The kinetic inertness results from the electronic configuration of the Cr ion (41). This type of orbital charge distribution makes ligand displacement and... 

Cobalt exists in the +2 or +3 valence states for the majority of its compounds and complexes. A multitude of complexes of the cobalt(III) ion [22541-63-5] exist, but few stable simple salts are known (2). Werner s discovery and detailed studies of the cobalt(III) ammine complexes contributed gready to modem coordination chemistry and understanding of ligand exchange (3). Octahedral stereochemistries are the most common for the cobalt(II) ion [22541-53-3] as well as for cobalt(III). Cobalt(II) forms numerous simple compounds and complexes, most of which are octahedral or tetrahedral in nature cobalt(II) forms more tetrahedral complexes than other transition-metal ions. Because of the small stabiUty difference between octahedral and tetrahedral complexes of cobalt(II), both can be found in equiUbrium for a number of complexes. Typically, octahedral cobalt(II) salts and complexes are pink to brownish red most of the tetrahedral Co(II) species are blue (see Coordination compounds). 

The coordination chemistry of NO is often compared to that of CO but, whereas carbonyls are frequently prepared by reactions involving CO at high pressures and temperatures, this route is less viable for nitrosyls because of the thermodynamic instability of NO and its propensity to disproportionate or decompose under such conditions (p. 446). Nitrosyl complexes can sometimes be made by transformations involving pre-existing NO complexes, e.g. by ligand replacement, oxidative addition, reductive elimination or condensation reactions (reductive, thermal or photolytic). Typical examples are ... 

A coordination compound, or complex, is formed when a Lewis base (ligand) is attached to a Lewis acid (acceptor) by means of a lone-pair of electrons. Where the ligand is composed of a number of atoms, the one which is directly attached to the acceptor is called the donor atom . This type of bonding has already been discussed (p. 198) and is exemplified by the addition compounds formed by the trihalides of the elements of Group 13 (p. 237) it is also the basis of much of the chemistry of the... 

Very recently, the coordination chemistry of low valent silicon ligands has been established as an independent, rapidly expanding research area. With the discovery of stable coordination compounds of silylenes [35-38], a major breakthrough was achieved. Within a short time a variety of stable complexes with a surprising diversity of structural elements was realized. Besides neutral coordination compounds (A, B) [35, 36, 38], and cationic compounds (C) [37], also cyclic bissilylene complexes (D) [39,40] exist. A common feature of the above-mentioned compounds is the coordination of an additional stabilizing base (solvent) to the silicon. However, base-free silylene complexes (A) are also accessible as reactive intermediates at low temperatures. 

Structural aspects and coordination chemistry of metal porphyrin complexes with emphasis on axial ligand binding to carbon donors and mono- and di-atomic nitrogen and oxygen donors. P. D. Smith, B. R. James and D. H. Dolphin, Coord. Chem. Rev., 1981,39, 31-75 (170). 

---