presentación

La Química,

la catálisis y la vida

Ernesto Carmona Guzmán

Universidad de Sevilla – Consejo Superior de Investigaciones Científicas

O

O

H

H

H

H

O

O

O

O

Fe Fe

O

O

C

C

O

O

C

C

Si

Si

O

O

O

O

O

O

O

O

C

C

O

O

1_{H +}1_{H =}2_{H + e}+ _+Q

2_{H +}1_{H =}3_{H +J}

3_{H +}3_{H =}4_{H + 2}1_H

41_H 4_{He + 2e}+ _{+ 2Q (26,72 MeV)}

(1)

(2)

« Before the word for it (in any language)

came to be, there was chemistry.

For one defining aspect of human

beings has always been

the meld of mind and hands

in transforming matter. »

Roald Hoffmann

Premio Nobel de Química 1981.

The New Chemistry. N. Hall, Ed.

Cambridge Univ. Press, 2000

D. Hodgkin

Nature, 2002, 418, 515

A. Corma, et al. Nature 2009, 458, 1154

La Química de

la Vida

QUÍMICA

Átomos,

Moléculas

Compuestos, materiales,...

N₂(g) + 3H₂(g) [cat] 2NH₃(g)

Industria

““

““

A

A

catalyst

catalyst

is

is

a

a

substance

substance

which

which

affects

affects

the

the

rate

rate

of

of

a

a

chemical

chemical

reaction

reaction

without

without

being

being

part

part

of

of

its

its

end

end

products

products

””

””

W.

W.

Ostwald

Ostwald

,

,

1900.

1900.

Premio

Premio

Nobel

Nobel

de

de

Qu

Qu

í

í

mica,

mica,

1909.

1909.

““

““

A

A

catalyst

catalyst

is

is

a

a

substance

substance

which

which

increases

increases

the

the

rate

rate

at

at

which

which

a

a

chemical

chemical

reaction

reaction

approaches

approaches

equilibrium

equilibrium

without

without

becoming

becoming

itself

itself

permanently

permanently

involved

involved

””

””

P.

W.

N.

M.

van

P.

W.

N.

M.

van

Leewen

Leewen

,

,

Homogeneous

Homogeneous

Catalysis

Catalysis

Kluwer

W.

W.

Crooks

Crooks

,

,

1898

1898

(68th

(68th

meeting

meeting

of

of

the

the

British

British

Association

Association

for

for

the

the

Advancement

Advancement

of

of

Science

Science

):

):

““

““

……

……

all

all

civilized

civilized

nations

nations

stand

stand

in

in

deadly

deadly

peril

peril

of

of

not

not

having

having

enough

enough

to

to

eat

eat

……

……

the

the

fixation

fixation

of

of

atmospheric

atmospheric

nitrogen

nitrogen

is

is

one

one

of

of

the

the

great

great

discoveries

discoveries

awaiting

awaiting

the

the

ingenuity

““

““

forhisstudiesofchemicalprocessesonsolid

for

his

studies

of

chemical

processes

on

solid

surfaces"

surfaces"

.

.

"in

recognition

of

their

contributions

to

the

invention

"inrecognitionoftheircontributionstotheinvention

and

development

of

chemical

high

pressure

methods"

anddevelopmentofchemicalhighpressuremethods"

"for

the

synthesis

of

ammonia

from

its

"forthesynthesisofammoniafromits

elements"

elements"

G.

G. ErtlErtl, Premio Nobel de Qu, Premio Nobel de Quíímica 2007mica 2007

C. Bosch, Premio Nobel de Qu

C. Bosch, Premio Nobel de Quíímica 1931 (F. mica 1931 (F. BergiusBergius))

F. Haber, Premio Nobel de Qu

Catalizadores

de

tres

v

Catalizadoresdetresv

í

í

as

as

A. Werner.

Premio Nobel de Química, 1913

M

L

L

L

L

L

L

M L

(O h)

M

L

L

L

L

M L

(T d)

CoCl

(N H

)

(am arillo)

CoCl

(N H

)

(púrpura)

CoCl

(N H

)

(verde y violeta)

CoCl

(N H

)

(dos isóm eros)

Cr

Fe

CH

W

CH

H

C

CH

CH

H

C

CO

Cr

CO

I

C

OC

CO

CH

₃

NH

Ru

NH

H

N

N

H

N

NH

N

Cl

Ti

Cl

P

P

Cl

CH

H CH

Xe

Au

Xe

Xe

Xe

2+

H

SiH

Mo

R

P

R

P

CO

PR

PR

O

Co

NH₃

H₃N NH₃ H₃N

CH₃

5+ NH₃

Co

O

H₃N NH₃ H₃N

CH₃

Algunos procesos catalíticos homogéneos

Catálisis Ziegler – Natta para la producción de poliolefinas (metalocenos como catalizadores).

Hidroformilación de alquenos catalizada mediante complejos de cobalto (CoH(CO)₄), o de rodio (RhH(CO)(PPh₃)₃). Síntesis de diversos productos oxigenados (alcoholes detergentes….).

Síntesis del ácido acético: Monsanto (Rh) y Cativa (Ir)

La Quiralidad es un fenómeno común en la naturaleza: Proteínas, Carbohidratos, Acidos Nucleicos

Las moléculas, como los objetos macroscópicos, tienen una estructura tridimensional. La quiralidad de una molécula es una consecuencia de su estructura espacial.

Productos Quirales: Efecto Biológico

H

X

Z

Y

Y' X'

H

X Y

Z

Y' X'

Z' Z'

A B

Enantiómeros y Propiedades Biológicas

>

Naproxeno

CO2H

MeO

Tóxico

CO2H

MeO

(R)-limonene (S)-limonene

mirror plane

Rh PPh₃

Ph₃P Cl

PPh₃ M P S S P + O O PPh₂ PPh₂ P Ph OMe P Ph MeO (Rh, Ir) (Osborn, Schrock) DIOP (Kagan)

Di PAMP (Knowles)

PPh₂

PPh₂

BINAP (Noyori)

P Ph OMe P Ph MeO Di PAMP (Knowles)

HO OH H C C N(H)C(O)R C(O)OR

1. H2, [Rh(DiPAMP)(S)2] +

2. H3O +

HO

OH CH2

C

H3N H

CO2

-L-dihidroxifenilalanina (L-DOPA)

W. Knowles, Monsanto (1974)

+

W. Knowles, R. Noyori, B. Sharpless, Premio Nobel de Química, 2001.

Importancia de los

Productos Quirales

en la Industria Farmacéutica

N OH HO COO -F NH O Ca2+ 2 H O O HO O O N H N _SO N

O _CF3 N

H N _SO N

O O

Total ventas productos 1-5:

17.600 millones

€

P Ph OMe P Ph MeO Di PAMP (Knowles)

HO OH H C C N(H)C(O)R C(O)OR

1. H2, [Rh(DiPAMP)(S)2] +

2. H3O +

HO

OH CH2

C

H3N H

CO2

-L-dihidroxifenilalanina (L-DOPA)

W. Knowles, Monsanto (1974)

+ NH₂ HO HO

Dopamina

L-Dopa

H₂N

HOOC OH

OH

D-Dopa

OH O

OH

HO NH2

[dopamina descarboxilasa]

NH2

OH HO

+ CO₂

L-dopa dopamina

OH O

HO H N CH3

HO

NH2

Richard F.

Richard F. HeckHeck

Ei

Ei--ichiichiNegishiNegishi

Akira Suzuki

Akira Suzuki

PREMIO NOBEL DE QU