Orbital octahedral complexes

In the case of the inner-orbital octahedral complexes, the six d sp hybrid orbitals are occupied by six electron pairs from ligands. The electrons of the central metal occupy the t2g orbitals. The inner orbital octahedral complexes which contain at least one d-orbital of t2g set empty are known to be labile. Probably, this empty d-orbital is used to accept the electron pair from the incoming hgand during the formation of an activated complex with a higher coordination number. In the inert inner-orbital octahedral complexes, every d-orbital of % set contains at least one electron. 

Explain inert and labile inner orbital octahedral complexes according to VBT. 

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... 

Fig. 2. Simplified molecular orbital diagram for a low spia octahedral complex, such as [Co(NH3 )g, where A = energy difference a, e, and t may be antisymmetric (subscript ungerade) or centrosymmetric (subscript, gerade) symmetry orbitals. See text.

Figure 19.14 Molecular orbital diagram for an octahedral complex of a first series transition metal (only a interactions are considered in this simplified diagram).

Thc Crystal l-ield Siabili2ation Energy (CFSl ) is the additional stability which accrues to an ion in a complex, as compared to the free ion, because its d-orbitals are split In an octahedral complex a l2 electron increases the stability by 2/5Ao and an Cf, electron decreases it by 3/5Ao- In a tetrahedral complex the orbital splitting is reversed and an e electron therefore increases the stability by 3/5At whereas a t2 electron decreases it by 2/5Ai. 

As six ligands approach a central metal ion to form an octahedral complex, they change the energies of electrons in the d orbitals. The effect (Figure 15.10, p. 419) is to split the five d orbitals into two groups of different energy. 

A theoretical basis for the description of the cationic complex [Cp Ru(PR3)2 = = SiR2]+ can also be given. For a d6 CpML2 system, a complete splitting of the three orbitals (octahedral symmetry) is to be expected. Consequently, a coordinated silylene ligand (without any base) should prefer the indicated (Fig. 10) conformation. 

In octahedral complexes, the e -orbitals (dz< and dx2 -yi) lie higher in energy than the t2 -orbitals (dxy, dyz, and dzx). The opposite is true in a tetrahedral complex, for which the ligand field splitting is smaller. 

FIGURE 16.36 I1ie tear-shaped objects are representations of the six ligand atomic orbitals that are used to build the molecular orbitals of an octahedral complex in ligand field theory. They might represent s- or p-orbitals on the ligands or hybrids of the two. 

For elements adjacent to the noble gases the principal orbitals used in bond formation are those formed by hybridisation of the s and p orbitals. For the transition elements there are nine stable orbitals to be taken into consideration, which in general are hybrids of five d orbitals, one s orbital, and three p orbitals. An especially important set of six bond orbitals, directed toward the comers of a regular octahedron, are the d2sps orbitals, which are involved in most of the Werner octahedral complexes formed by the transition elements. 

Now look at octahedral complexes, or those with any other environment possessing a centre of symmetry e.g. square-planar). These present a further problem. The process of violating the parity rule is no longer available, for orbitals of different parity do not mix under a Hamiltonian for a centrosymmetric molecule. Here the nuclear arrangement requires the labelling of d functions as g and of p functions as m in centrosymmetric complexes, d orbitals do not mix with p orbitals. And yet d-d transitions are observed in octahedral chromophores. We must turn to another mechanism. Actually this mechanism is operative for all chromophores, whether centrosymmetric or not. As we shall see, however, it is less effective than that described above and so wasn t mentioned there. For centrosymmetric systems it s the only game in town. 

We are now ready to apply the ideas in the preceding three sections to the construction of molecular orbitals in octahedral complexes. 

Warren KD (1984) Calculations of the Jahn-Teller Coupling Constants for d Systems in Octahedral Symmetry via the Angular Overlap Model. 57 119-145 Warren KD (1977) Ligand Field Theory off-Orbital Sandwich Complexes. 33 97-137 Warren KD (1976) Ligand Field Theory of Metal Sandwich Complexes. 27 45-159 Watson RE, Perlman ML (1975) X-Ray Photoelectron Spectroscopy. Application to Metals and Alloys. 24 83-132... 

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