Coordination compounds electronic structures

Coordination Organometalhc Chemistry Principles Electronic Structure of Main-group Compounds Electronic Structure of OrganometaUic Compounds Electronic Structure of Clusters Ligand Field Theory Spectra Molecular Orbital Theory Symmetry Point Groups. 

Carbene Complexes Carbonyl Complexes ofthe Transition Metals Cyanide Complexes of the Transition Metals Dinuclear Organometallic Cluster Complexes Electron Transfer in Coordination Compounds Electron Transfer Reactions Theory Electronic Structure of Organometallic Compounds Luminescence Nucleic Acid-Metal Ion Interactions Photochemistry of Transition Metal Complexes Photochemistry of Transition Metal Complexes Theory Polynuclear Organometallic Cluster Complexes. 

For the higher activity Ziegler-Natta catalysts (Table II) based on reaction products of specific magnesium, titanium, and aluminum compounds, the similarity in size, coordination preference, electronic structure, and electronegativity of Ti(IV), Mg(II), and Al(III) ions is reflected in structural parameters and chemical properties (38) (Table III). The similarity in size between Mg(II) and Ti(IV) probably permits an easy substitution between ions in a catalyst framework. 

The period under discussion has seen intense interest in the recently discovered i7 -H2 complexes. The relevance of these to some isomerization reactions of square-planar complexes was reported in Volume 5 of this series, and is covered in another recent review. " More of these fluxional ds-dihydridoplatinum compounds have been reported, and the role of 17 -H2 derivatives in oxidative additions to d rhodium(I) and iridium(I) has been discussed. The increasing role of theoretical and bonding studies is reflected in four works relevant to 4-and 5-coordinate molecules. Electronic structure is related to chemical reactivity in the reactions of phosphine bases with d bis(l,l-dithiolato)platinum com-plexes. Huckel calculations on the reactions of bis(nitrogen donor) ligands with 16-electron platinum(II) complexes have been carried out, as has more work on symmetry selection rules for isomerization reactions, which includes pseudorotation of 5-coordinate complexes and square-planar to tetrahedral conversions of 4-coordinate molecules. ... 

Free Radicals. In the formula of a polyatomic radical an unpaired electron(s) is(are) indicated by a dot placed as a right superscript to the parentheses (or square bracket for coordination compounds). In radical ions the dot precedes the charge. In structural formulas, the dot may be placed to indicate the location of the unpaired electron(s). 

Molecular and electronic structures of penta- and hexa-coordinate silicon compounds. S. N. Tan-dura, M. G. Voronkov and N. V. Alekseev, Top. Curr. Chem., 1986,131, 99 (1008). 

Gas phase U. V. photoelectron spectroscopy as a tool for the investigation of electronic structures of coordination compounds. C. Cauletti and C. Farlani, Comments Inorg. Chem., 1985, 5, 29 (95). 

Earlandite structure, 6,849 Edge-coalesced icosahedra eleven-coordinate compounds, 1, 99 repulsion energy coefficients, 1,33,34 Edta — see Acetic acid, ethylenediaminetetra-Effective atomic number concept, 1,16 Effective bond length ratios non-bonding electron pairs, 1,37 Effective d-orbital set, 1,222 Egta — see Acetic acid,... 

The striking feature of many coordination compounds is that they are colored or paramagnetic or both. How do these properties arise To find out, we need to understand the electronic structures of complexes, the details of the bonding, and the distribution of their electrons. 

Coordination compounds of dianionic dithiolene (S2C2 R2) and benzene-1,2-dithiolene (bdt = (S2C6H4) and their derivatives have been studied since the 1960s by Mossbauer spectroscopy [87] and other techniques. Nevertheless, many aspects of their electronic structure remained uncertain for a long time. The five-coordinate ferric complexes with two equatorial dithiolene ligands exhibit intermediate spin and show the Mossbauer parameters = 0.25-0.38 mm s and A q = 1.6-3.2 mm s For example, [Fe° mnt)2/ y] with two mnt ligands (=S2C2(CN)2) and an... 

The intermediate-spin ground state of the ferric compounds published by Jager and coworkers is also stabilized by a N4-macrocyclic ligand, [N4] which exist in different varieties of substitutions. The apical ligands are weakly coordinating halides or pseudohalides, such as iodide in the case of [Fe [N4]l] (20) [68]. The electronic structure was elucidated by EPR, Mbssbauer and DFT studies. 

In a crystal-field picture, the electronic structure of iron in the five-coordinate compounds is usually best represented by a (d yf idyz, 4cz) ( zO configuration [66, 70], as convincingly borne out by spin-unrestricted DFT calculations on the Jager compound 20 [68]. The intermediate spin configuration with an empty d 2 yi orbital in the CF model, however, has a vanishing valence contribution to the... 

Most tin(II) compounds display structures with a trigonal pyramidal coordination. This is of course to be expected as the tin atom is in the first place electrophilic in order to complete its outer electron configuration (cf. Chapter 5 and 6). To illustrate the resemblance of this geometry between ionic and molecular compounds, the structure of NH4SnF3 (5) 31) is compared with that of the cage compound (Me3CN)3(Me3A10)Sn4 (6) 32). The coordination sphere of the tin atom is the same in 5 and 6 (for the complete structure of 6 see Sect. 6.5) ... 

Square-planar zinc compounds predominate with these ligand types as would be predicted. This is in contrast to the prevalence of tetrahedral or distorted tetrahedral geometries for four-coordinate species that have been discussed thus far. Zinc porphyrin complexes are frequently used as building blocks in the formation of supramolecular structures. Zinc porphyrins can also act as electron donors and antenna in the formation of photoexcited states. Although the coordination of zinc to the porphyrin shows little variation, the properties of the zinc-coordinated compounds are extremely important and form the most extensively structurally characterized multidentate ligand class in the CSD. The examples presented here reflect only a fraction of these compounds but have been selected as recent and representative examples. Expanded ring porphyrins have also... 

Perhaps the greatest area in which the Lewis acid-base approach is most useful is that of coordination chemistry. In the formation of coordination compounds, Lewis acids such as Cr3+, Co3+, Pt2+, or Ag+ bind to a certain number (usually 2, 4, or 6) of groups as a result of electron pair donation and acceptance. Typical electron pair donors include H20, NH3, F , CN , and many other molecules and ions. The products, known as coordination compounds or coordination complexes, have definite structures that are predictable in terms of principles of bonding. Because of the importance of this area of inorganic chemistry, Chapters 16 through 22 in this book are devoted to coordination chemistry. 

Although the simple valence-bond approach to the bonding in coordination compounds has many deficiencies, it is still useful as a first attempt to explain the structure of many complexes. The reasons why certain ligands force electron pairing will be explored in Chapter 17, but it is clear that high- and low-spin complexes have different magnetic character, and the interpretation of the results of this technique will now be explored. 

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