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pptx
5-Sep-10
p1
04-Ktt212-18elect-09.pptx
5-Sep-10
Cr(CO)6
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
p2
04-Ktt212-18elect-09.pptx
5-Sep-10
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
Slide 6
p3
04-Ktt212-18elect-09.pptx
5-Sep-10
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
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
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
p4
04-Ktt212-18elect-09.pptx
5-Sep-10
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
p5
04-Ktt212-18elect-09.pptx
5-Sep-10
p6
04-Ktt212-18elect-09.pptx
5-Sep-10
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
p7
04-Ktt212-18elect-09.pptx
5-Sep-10
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
[PtCl4]2:
[Mn(CO)5]:
p8
04-Ktt212-18elect-09.pptx
5-Sep-10
OC
OC
Mn
Mn
CO
O C Co C O Co
CO
OC CO OC CO
OC
CO CO
Slide 17
OC
(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
p9
04-Ktt212-18elect-09.pptx
5-Sep-10
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
Slide 20
p10
04-Ktt212-18elect-09.pptx
5-Sep-10
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
3 4 6 8 10
Slide 22
p11
04-Ktt212-18elect-09.pptx
5-Sep-10
Slide 23
OC OC OC Fe OC
O C Fe
CO CO CO H
Ph3 P Ni Ni P Ph3
p12
04-Ktt212-18elect-09.pptx
5-Sep-10
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
Slide 26
p13
04-Ktt212-18elect-09.pptx
5-Sep-10
OC OC OC Fe OC
O C Fe
CO CO CO H
p14