Inorganic complexes, molecular orbital

Carbonyl Complexes of the Transition Metals Coordination Numbers Geometries Coordination Organometalhc Chemistry Principles Diffraction Methods in Inorganic Chemistry Molecular Orbital Theory. 

E. Basolo and R. G. Pearson, Mechanisms of Inorganic Reactions, 2nd ed., John Wiley Sons, Inc., New York, 1967. An excellent volume that stresses the reactions of complexes ia solution a background and a detailed theory section is iacluded that is largely crystal field theory, but some advantages and disadvantages of molecular orbital theory are iacluded. 

Most stable ground-state molecules contain closed-shell electron configurations with a completely filled valence shell in which all molecular orbitals are doubly occupied or empty. Radicals, on the other hand, have an odd number of electrons and are therefore paramagnetic species. Electron paramagnetic resonance (EPR), sometimes called electron spin resonance (ESR), is a spectroscopic technique used to study species with one or more unpaired electrons, such as those found in free radicals, triplets (in the solid phase) and some inorganic complexes of transition-metal ions. 

Figure 7.21 (A) Formation of the [Fe" =0(TMP ")] complex using the TMP ligand. (B) Molecular orbital diagram describing bonding in the [Fe" =0(TMP )] complex. (Adapted with permission from Scheme 4 and Figure 2 of reference 68. Copyright 1997, Society of Biological Inorganic Chemistry.)...

It is apparent that the molecular orbital theory is a very useful method of classifying the ground and excited states of small molecules. The transition metal complexes occupy a special place here, and the last chapter is devoted entirely to this subject. We believe that modem inorganic chemists should be acquainted with the methods of the theory, and that they will find approximate one-electron calculations as helpful as the organic chemists have found simple Hiickel calculations. For this reason, we have included a calculation of the permanganate ion in Chapter 8. On the other hand, we have not considered conjugated pi systems because they are excellently discussed in a number of books. 

This technique has been used extensively as an experimental comparison for one or other of the types of theoretical molecular orbital calculations for organic and some nonmetallic inorganic compounds. However, for transition metal complexes and cluster compounds, their lower volatility presents some difficulties, and for the photoelectron spectra of the cluster alkyne complexes that have been recorded a heated inlet probe has been used to overcome this problem. 

Molecular Orbital Theory Phosphoms Inorganic Chemistry Polynnclear OrganometaUic Clnster Complexes. 

The classical Dewar-Chatt-Duncanson model for metal-alkene bonding has been revisited with a combination of X-ray structural data (see Diffraction Methods in Inorganic Chemistry) and DFT calculations (see Molecular Orbital Theory), particularly on complexes of the type (acac)Rh(alkene)2. These indicate the existence of distortions from idealized geometry involving a twist (127), where the axis of the double bond is no longer perpendicular to the molecular plane and a roll (128), where the line... 

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