Coordination Chemistry Reactions of Metal Complexes

0
0
1938 days ago, 648 views
PowerPoint PPT Presentation
Substitution responses. . Labile buildings <==> Fast substitution responses (< few min)Inert edifices <==> Slow substitution responses (>h)a dynamic idea. Not to be confounded withstable and temperamental (a thermodynamic idea DGf <0). Systems of ligand trade reactionsin octahedral edifices.

Presentation Transcript

Slide 1

Coordination Chemistry Reactions of Metal Complexes

Slide 2

Substitution responses Labile buildings <==> Fast substitution responses (< few min) Inert edifices <==> Slow substitution responses (>h) a motor idea Not to be mistaken for steady and flimsy (a thermodynamic idea D G f <0)

Slide 3

Dissociative (D) Associative (An) Interchange (I) Mechanisms of ligand trade responses in octahedral buildings I an if affiliation is more critical I d if separation is more essential

Slide 5

Kinetics of dissociative responses

Slide 6

Fast harmony K 1 = k 1/k - 1 k 2 << k - 1 Kinetics of trade responses For [Y] >> [ML 5 X]

Slide 7

Kinetics of acquainted responses

Slide 8

Principal instruments of ligand trade in octahedral edifices Dissociative Associative

Slide 9

MOST COMMON Dissociative pathway (5-composed middle of the road) Associative pathway (7-facilitated moderate)

Slide 10

Experimental confirmation for dissociative components Rate is free of the way of L

Slide 11

Experimental proof for dissociative systems Rate is subject to the way of L

Slide 12

Inert and labile buildings Some basic thermodynamic and dynamic profiles Exothermic (favored, extensive K ) Large E a , moderate response Stable transitional Exothermic (favored, huge K ) Large E a , moderate response Endothermic (disfavored, little K ) Small E a , quick response

Slide 13

Labile or latent? LFAE = LFSE(sq pyr) - LFSE(oct)

Slide 14

Inert ! Why are a few designs inactive and some are labile?

Slide 15

Substitution responses in square-planar buildings the trans impact (the capacity of T to labilize X)

Slide 16

Synthetic uses of the trans impact

Slide 17

Mechanisms of ligand trade responses in square planar edifices

Slide 18

M 1 (x +1)+ L n + M 2 (y-1)+ L' n M 1 (x+) L n + M 2 (y+) L' n Electron exchange (redox) responses - 1e (oxidation) +1e (lessening) Very quick responses (substantially quicker than ligand trade) May include ligand trade or not Very critical in organic procedures (metalloenzymes)

Slide 19

Outer circle system [Fe(CN) 6 ] 3-+ [IrCl 6 ] 3-[Fe(CN) 6 ] 4-+ [IrCl 6 ] 2-[Co(NH 3 ) 5 Cl] + [Ru(NH 3 ) 6 ] 3+ [Co(NH 3 ) 5 Cl] 2+ + [Ru(NH 3 ) 6 ] 2+ Reactions ca . 100 circumstances quicker than ligand trade (coordination circles continue as before) r = k [A][B] Tunneling component

Slide 20

Inner circle instrument [Co(NH 3 ) 5 Cl)] 2+ :::[Çr(H 2 O) 6 ] 2+ [Co(NH 3 ) 5 Cl)] 2+ + [Çr(H 2 O) 6 ] 2+ [Co III (NH 3 ) 5 ( m - Cl ) Çr II (H 2 O) 6 ] 4+ [Co(NH 3 ) 5 Cl)] 2+ :::[Çr(H 2 O) 6 ] 2+ [Co II (NH 3 ) 5 ( m - Cl ) Çr III (H 2 O) 6 ] 4+ [Co III (NH 3 ) 5 ( m - Cl ) Çr II (H 2 O) 6 ] 4+ [Co II (NH 3 ) 5 ( m - Cl ) Çr III (H 2 O) 6 ] 4+ [Co II (NH 3 ) 5 (H 2 O)] 2+ + [çr III (H 2 O) 5 Cl] 2+ [Co II (NH 3 ) 5 (H 2 O)] 2+ [Ço(H 2 O) 6 ] 2+ + 5NH 4 +

Slide 21

Inner circle system Reactions considerably speedier than external circle electron exchange (crossing over ligand frequently traded) r = k' [Ox-X][Red] k' = ( k 1 k 3/k 2 + k 3 ) Tunneling through scaffold component

SPONSORS