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Introduction to Structure and Bonding

The organic chemistry at the some point extended to the molecular level, because physical and chemical properties of are ultimately explained in terms of the structure and bonding of molecules. This part of organic chemistry introduces the fundamental facts and principles that are needed for discussion of organic molecules.

Categories of Ligand Coordination

There are three categories of ligands:

L:  neutral electron pair donor (i.e., CO, PR3)

X:  an anionic electron pair donor (i.e., X-, H-)

M-M:  neutral 1 electron donor

Differentiate the ligand L-type from the ligand X-type ligands:  To differentiate between X and L type ligands, consider eliminate the ligand from the metal center with the ligand taking the electron pair in the M-L bond.  If the ligand in its free state is neutral, it is the L-type ligand.  It is of X-type if it would be anionic.

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Ligands that donate more than one pair of the electrons can be classified using L and X designations:

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Types of ligand coordination:

Terminal:  This is the first category of ligand and is bound to only one metal center (L-M or X-M).

Bridging (µ):  unlike the Terminal the Bridging Ligand is attached to two different metal centers (M-L-M' or M-X-M').  L-type ligands, lone pair are usually shared between the two metals (count 1 electron for each one of the metal).  For X- type ligands, lone pair can also be shared.  If X-type ligand has additional lone pairs (i.e., halide, alkoxides), then to coordinate to the second metal centre the additional lone pairs can be used.

Hapticity (η):  this is another type of ligand and is attached to a metal center through more than one atom. it is used to illustrate ligands with conjugated π-systems.

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The 18-Electron Rule

Remember: octet rule- First row elements can accommodate up to 8 valence electrons because they have 4 valence orbitals (1 s + 3 p).

Transition metals have 9 valence orbitals (1 s + 3 p + 5 d).  Upon bonding to a ligand set, there will be a sum of the 9 low lying orbitals. 18-Electron Rule -- we can expect that the low lying MOs can accommodate up to 18 valence electrons.  Organometallic complexes with the 18 electrons are predicted to be stable because they will have electron's closed shell.  Complexes with the 18 electrons are frequently referred to as being coordinatively saturated.

Counting electrons: For counting the electrons there are two models.  Both provides the same answer, but offer different- different advantages and disadvantages. 

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