04-Ktt212-18elect-09.

pptx

5-Sep-10

The 18 electron rule

For organic chemists its the octet rule, for organometallic chemists its the 18 electron rule. Useful for purposes of predicting reactivity. Each derives from a simple count of the number of electrons that may be accommodated by the available valence orbitals (one s and three p for organic chemists; organometallic chemists get five bonus dorbitals in which to place their electrons).
Slide 1

The 18 electron rule

states will follow the 18electron rule; metals in earlier rows and endrows do not. high field ligands will also observe the 18 electron rule.(later in the course) stability of complex.

Organometallic complexes with oxidation Complexes with backbonding electron or

18electron rule can assist in predicting the

Slide 2

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What is the 18 Electron Rule?

n + 2(CN) = 18

n = the number of valence d electrons on the metal CN is the coordination number

this 'rule' arise from the closed shell configuration d10s2p6 (Noble gas rule) analogous to octet rule for main group applies to most organometallic compounds
Slide 3

Cr(CO)6

Cr (0) a d6 central metal 6 CO with 2 e per CO

6 12

18

Cr(CO)7 [Cr(CO)6]

Cr (0) a d6 metal 7 CO with 2 e per CO Cr (0) a d6 metal 6 CO with 2 e per CO cas neg.

6 14 6 12 1

20

19

Slide 4

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CH3Re(CO)5 Re(I) CH3 donates 2 elect. 5 carbonyls (CO) Cp2Ru Ru(II) = 6 2 Cp with 6 elect. (2*(5 + 1)) = 12 Fe(0) Fe2(CO)9 3 terminal CO gives 2 elec. 3 bridging CO gives 1 elec. FeFe bond gives 1 elec. Cr(0) Cr(CO)6 6 Co gives 2 elec. each

6 2 10 6 12 8 6 3 1 6 12

18

18

18

18
Slide 5

Ru(II) = 6 2 Cp with 6 elect. (2*(5 + 1)) = 12

Fe OS = 0; No. of electrons = 8 3 bridging COs; 3*1 = 3

3 terminal COs; 3*2 = 6

Slide 6

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We can predict that less stable complexes are due to number of electrons; complexes can be stabilized by adding or removing electrons. Complexes that do not obey the rule will undergo reactions to provide a situation whereby the rule is observed: 1. V(CO)6 17elec. will oxidize [V(CO)6] which is an 18electron system. 2.[Fe(C5H5)2]+ with 17elec. will be reduced Fe(C5H5)2 which obeys the 18electron
Slide 7

* No of electrons 1st row

3 Sc Y (La)

4 Ti Zr Hf

5 V Nb Ta

6 Cr Mo W

7 Mn Tc Re

8 Fe Ru Os

9 Co Rh Ir

10 Ni Pd Pt

11 Cu Ag Au

12 Zn Cd Hg

2nd row

3rd row

Oxidation State

No of electrons on the metal ions

O I II III IV

3 2 1 0

4 3 2 1 0

5 4 3 2 1

6 5 4 3 2

7 6 5 4 3

8 7 6 5 4

9 8 7 6 5

10 9 8 7 6

11 10 9 8 7

12 11 10 9 8
Slide 8

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Knowing how many valence electrons "belong to" a transition metal complex allows us to make predictions about the mechanisms of reactions and the possible modes of reactivity.

There are two distinct methods that are used to count electrons, (i) the neutral or covalent method and (ii) the effective atomic number (EAN) or ionic method. These are simply two different accounting systems that give us the same final answer.
Slide 9

Slide 10

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Method 1: The ionic (charged) model

The basic premise of this method is that (i) we remove all of the ligands from the metal and (ii) add the proper number of electrons to each ligand to bring it to a closed valence shell state. 1. E.g. we remove ammonia(NH3) from metal complex, NH3 has a completed octet and acts as a neutral molecule. 2. When it bonds to the metal center it does so through its lone pair (Lewis acidbase adduct). 3. We call ammonia a neutral twoelectron donor.
Slide 11

Condt Method 1: The ionic (charged) model

In contrast, if we remove a methyl group from the metal and complete its octet, then we formally have CH3. If we bond this methyl anion to the metal, the lone pair forms our metalcarbon bond and the methyl group acts as a twoelectron donor ligand. Notice that to keep charge neutrality we must oxidize the metal by one electron (i.e. assign a positive charge to the metal). This will reduce the delectron count of the metal center by one.
Slide 12

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Condt Method 2: The covalent (neutral) model

In this method, we remove all of the ligands from the metal, & we do whatever is necessary to make them neutral, e.g. ammonia, NH3
When removed from the metal, it is a neutral molecule with one lone pair of electrons.

NH3 is a neutral two electron donor as with the ionic model.

Slide 13

We diverge from the ionic model when we consider a ligand such as methyl.
When we remove it from the metal and make the methyl fragment neutral, we have a neutral methyl radical. Both the metal and the methyl radical must donate one electron each to form our metalligand bond. Therefore, the methyl group is a one electron donor, not a two electron donor as it is under the ionic formalism. Where did the other electron "go"? It remains on the metal and is counted there.

In the covalent method, metals retain their full complement of d electrons because we never change the oxidation state from zero; i.e. Fe will always count for 8 electrons
regardless of the oxidation state and Ti will always count for four.
Slide 14

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Notice that this method does not give us any immediate information about the formal oxidation state of the metal, so we must go back and assign that in a separate step. For this reason, many chemists (particularly those that work with high oxidation state complexes) prefer the ionic method.
Slide 15

(a) 10 e (Pt) + 4 e (4 Cl) + 2 e (charge 2) = 16 e (b) 8 e (Pt2+) + 8 e (4 Cl) = 16 e

[PtCl4]2:

[Mn(CO)5]:

(a) 7 e (Mn) + 10 e (5CO) + 1 e(charge 1) = 18 e (b) 8 e (Mn) + 10 e (5 CO) = 18 e

Slide 16

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[Mn2(CO)10] : 14 e (2 Mn) + 20 e (10 CO) + 2 e (Mn Mn) = 36 e (i.e., 18 e per Mn)

[Co2(CO)8]: 18 e (2 Co) + 16 e (8 CO) + 2 e (CoCo) = 36 e (i.e., 18 e per Co)

OC CO OC CO

OC

OC

Mn

Mn

CO

O C Co C O Co

CO
OC CO OC CO

OC

CO CO
Slide 17

OC

Electron counting for [Rh2Cl2(CO)4]:

(a) 18 e (2 Rh) + 8 e (4 CO) + 6 e (2 bridging Cl) = 32 e (i.e., 16 e per Rh) (b) 16 e (2 Rh+) + 8 e (4 CO) + 8 e (2 bridgingCl) = 32 e (i.e., 16 e per Rh)

Slide 18

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(C5H5)Fe(CO)2Cl Fe(II) 6 e (C5H5) 6 e 2(CO) 2 x 2 = 4 e Cl 2 e Total 18 e : Electron Counting: Donor Pairs

Fe Cl

CO CO
Slide 19

[Fe(CO)4]2 Fe(2) d10 thus 10 +2(4) = 18 Fe2(CO)9 Fe(0) d8 thus: 2 metals 2(8) + CO ligands 9(2) MM bond 2 Total = 36 can view bridging CO; as 3 center 2 electron bond

OC OC OC Fe

O C C Fe O C O

CO CO CO
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Slide 21

Ligands
H-, [alkyl]- e.g. ([CH3]-, [C2H5]- dsb.), [aryl]- e.g. ([C6H5]-, [C6H5CH2]-, etc., CO, CS, CSe, PR3, P(OP)3, SbR3, F-, Cl-, Br-, I-, carbene(=CR2), alkene NO, NS, carbienes(CR) Dienes, [-allyl]-, [C5H5]-, [C4H4]2-, [C7H7]+ arene(C6H6, C6H5CO2CH3, etc.) [C3H3]3teraenes(C8H8) [C8H8]22

No. of electrons donated

3 4 6 8 10

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Slide 23

OC OC OC Fe OC

O C Fe

CO CO CO H

Fe = 8 e3 terminal CO = 6 eFe-Fe = 1 e1 H = 1 e2 CO = 2eTotal = 18 e-

Ph3 P Ni Ni P Ph3

Ni = 10 e5 -C5H5 = 5 e2-PPh3 = 3 Total = 18 eSlide 24

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Slide 25

Cr OC OC
Cr = 6 e6 -C6H6 = 6 e3 CO = 3*2 = 6 eTotal = 18 e-

OC Rh OC

Cl Rh Cl

CO

CO

CO

Rh = 9 e-Cl (1 e- Rh# 2 e- Rh##) = 3 e2CO = 4 eTotal = 16 e-

Slide 26

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OC OC OC Fe OC

O C Fe

CO CO CO H

Fe = 8 e3 terminal CO = 6 eFe-Fe = 1 e1 H = 1 e2 CO = 2eTotal = 18 eSlide 27

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