Metal-Ligand Bonding by E.A. Moore, R. Janes

By E.A. Moore, R. Janes

To understand the chemistry and actual homes of complexes of the transition sequence, an knowing of metal-ligand interactions utilized to complexes of the d-block is required. steel Ligand Bonding goals to supply this via an available, particular, non-mathematical technique. preliminary chapters aspect the crystal-field version, utilizing it to explain using magnetic measurements to tell apart complexes with varied digital configurations and geometries. next chapters examine the molecular orbital conception of transition steel complexes utilizing a pictorial strategy. Bonding in octahedral complexes is explored and digital spectra and magnetic houses are given large assurance. the fabric addressed during this publication types the root of undergraduate lecture classes on d-block chemistry and allows studying via a variety of key good points, together with: complete color diagrams; in-text questions with solutions; revision routines and obviously outlined studying results to motivate a reflective method of examine; an linked site; and experimental facts and observations from way of life. A uncomplicated wisdom of atomic and molecular orbitals as utilized to major workforce parts is thought.

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For such complexes, the eg* level is above the t2g*level. n-bonding ligand orbitals are at the same energy, the o-bonded egorbitals will lie below the n;-bonded t orbitals. Consequently, 24 the antibonding eg* orbitals will lie above the antibonding t2g*orbitals. There are six ligands, each with two n;-bonding orbitals. Of these twelve n-bonding orbitals, three overlap with metal d orbitals to form the t and t2g*orbitals. The 2g. other nine remain as non-bonding ligand orbitals. In addition, each ligand has one filled o-bonding orbital, making a total of six filled o-bonding orbitals.

9 2 ~What ~ . is the electronic configuration of the metal ion? Cobalt(I1) complexes have seven 3d electrons. , with three unpaired electrons. In a strong field, the configuration would be t2,"eg1,with only one unpaired electron. 1 . 9 2 is~ close ~ to the spin magnetic moment for one unpaired electron, and so we can conclude that this is a strong-field complex. 2 shows the observed magnetic moment (A,,,) ranges for octahedral (weak field) and tetrahedral complexes for first-row transition-metal elements in their common oxidation states.

3 Orbital energy-level diagram (showing 3d orbitals only) for (a) a free ion, (b) an ion in a sphere of negative charge and (c) an ion in a tetrahedral complex. 29 The colours of tetrahedral complexes are far more intense than their octahedral counterparts at the same concentration. This is because they do not possess a centre of symmetry, and, consequently, the Laporte selection rule is not strictly applicable. This is discussed in more detail in Section 11 using the molecular orbital approach.

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