STATE TO EXPLAIN..... Noble Metal Nobel prize Nobel  Laureates Nobel Prize for Noble Metal Advance Metal catalyzed reaction

1. Noble Metal to Nobel Prize
Dr. Sujitlal Bhakta

2. STATE TO EXPLAIN …….
 Noble Metal
 Nobel prize
 Nobel Laureates Nobel Prize for Noble Metal
 Advance Metal catalyzed reaction

3. NOBLE METALS
 Noble metals are the metal elements that resist oxidation,
tarnish and corrosion during heating, casting or soldering
and when used intraoral.
e.g., gold and platinum
 Platinum, Ruthenium, Rhodium, Palladium, Silver,
Osmium, Iridium and Gold are the Eight Nobel metals.

4.  Good metallic surface that retain their surface in dry air.
NOBLE METALS

6. The oxidation state of Ruthenium ranges from
0 to +8 and −2. The +2, +3 and +4 states are the
most common.
In 2007 Nobel Prize in Physics was awarded
to Albert Fert and Peter Gruenberg for the discovery
of GMR.
Ruthenium(Ru)

7. It is compatible with semiconductor
processing techniques; used in microchips and
for the giant magneto resistive(GMR) read
element for hard disk drives.

8. Rhodium(Rh)
Rhodium is a noble metal, resistant to
corrosion.
The common oxidation state of
Rhodium is +3, but oxidation states from
+0 to +6 are also observed.

9. Rhodium is used as an alloying
agent for hardening and
improving the corrosion
resistance.
These alloys are used in
furnace windings, bushing for
glass fibers, production, thermo-
couple elements electrodes for
aircraft spark plugs and
laboratory crucibles.

10. Palladium(Pd)
 Common oxidation states of palladium are 0, +1,
+2 and +4. There are relatively few known
compounds with palladium unambiguously in the +3
oxidation state.
 Palladium does not react with oxygen at normal
temperature.
 Application of palladium in electronics is in the
manufacture of multilayer ceramic capacitors.

12. Silver(Ag)
 The most common oxidation state of silver
is +1 and less common +2,+3 and even +4.
Silver is a noble metal, resistant to corrosion.
Wound dressings.

13. Silver and silver alloys are used
in the construction of high-quality
musical wind instruments of many
types.
Silver's catalytic properties make
it ideal for use as a catalyst in
oxidation reactions.

14. Osmium(Os)
Osmium forms compounds with oxidation
states ranging from −2 to +8.
The most common oxidation states are +2,
+3, +4 and +8.
Osmium tetroxide has been used
in fingerprint detection.
 Strong oxidant.

15. Iridium(Ir)
Iridium forms compounds in oxidation
states between −3 and +9; the most
common oxidation states are +3 and +4.
Their resistance to arc erosion makes
Iridium alloys ideal for electrical
contacts for spark plugs and Iridium-
based spark plugs are particularly used in
aviation.

16. Platinum(Pt)
Platinum is a noble and precious metal
meaning that it will not easily dissolve in any
solvent or in rust.
The most common oxidation states of Platinum
are +2 and +4. The +1 and +3 oxidation states are
less common.
 Platinum is sensitive to the high temperature.
Platinum is a very good oxidation catalyst and
has good resistance to poisons such as sulphur,
phosphorus or lead which may be present in the
exhaust.

17. Gold(Au)
It is one of the least reactive chemical
elements and is solid under standard
conditions.
The oxidation state of Gold in its
compounds ranges from −1 to +5, but Au(I)
and Au(III) dominate its chemistry.
Gold is unaffected by oxygen at any
temperature.
 Gold does not react with ozone.

18. Uses NOBLE METALS

19. THE HISTORY OF
NOBEL PRIZE

20. Alfred Nobel was born on 21 October 1833
in Stockholm, Sweden into a family of engineers.
He was a chemist, engineer and inventor.
Alfred Nobel was died at San Remo, Italy, on 10
December, 1896
History of Nobel prize

21. He will of the Swedish chemist Alfred Nobel, the
inventor of Dynamite, established the prizes in 1895
It was first awarded in Physics, Chemistry,
Physiology or Medicine, Literature and Peace in
1901 and the annual Prize Award Ceremony on
December 10, the anniversary of Nobel’s death.
In Economic Sciences was established by Sweden's
central bank in 1968.
History of Nobel prize ...

22. The Introduction of the Nobel Prize
Ceremony
Date
Frequency
Place
Prizes
Activities
Guests
Dec.10th.
Once a year
The Stockholm Concert Hall(Sweden)
and for the peace prize which is held
in Oslo, Norway
Diploma, Gold medal
Presentation, banquet
Winners (families), King & Queen,
leaders, students

23. Chemistry behind the Dynamite
Nitroglycerine, a highly explosive liquid.
Nitroglycerine was produced by mixing glycerine
with sulfuric and nitric acid.
Mixing nitroglycerine with kieselguhr would turn
the liquid into a paste which named as Dynamite.
……. Alfred Nobel, the inventor of Dynamite

24. DYNAMITE …
HO
OH
OH
HNO3, H2SO4
O
O
O
NO2
O2N
NO2
Nitroglycerineglycerine
O
O
O
NO2
O2N
NO2
Nitroglycerine
Mixing
O2Si
Kieselguhr
Paste
Dynamite

25. A. Diagram Sawdust (or any other type of
absorbent material) soaked in
nitroglycerin.
B. Protective coating surrounding the
explosive material.
C. Blasting cap.
D. Electrical cable (or fuse) connected to
the blasting cap.
DYNAMITE …

26. NOBEL
Laureates
NOBEL PRIZE for
Noble Metal

27.  E. O. Fisher, G. Wilkinson (1973)
Sandwich compounds
 K. B. Sharpless, R. Noyori (2001)
Hydrogenation and oxidation
Yves Chauvin, Robert H. Grubbs, Richard R. Schrock (2005)
Metal-catalyzed alkene metathesis
 Richard F. Heck, Ei-ichi Negishi and Akira Suzuki (2010)
for the development of palladium-catalyzed cross couplings in
organic synthesis
Nobel Laureates …

28. Rh(I)/ (III) Direct C-H
Funtionalization
R B
OH
OH
X B
OH
OH
R Rh(I)
Aldol-type
Mannich-type
1,4- addition
Hydrogenation
H2
C-X, C-O Cleavage
C-N, C-C Cleavage
Isomerization Yn-En
Rhodium-Catalyzed Reaction

29. Rhodium-Catalyzed Reaction
Geoffrey Wilkinson
Hydrogenation of
Unsaturated Hydrocarbons

30. PPh3
Rh H
PPh3
Cl
H
PPh3
Rh H
PPh3
Cl
H
R
R
H
H
coordination
R
migratory
insertion
reductive
elimination
oxidative
addition
-PPh3
+PPh3
[RhCl(PPh3)2] RhCl(PPh3)3
H H
PPh3
Rh H
PPh3
H
Cl
R
R'
R'
R'
R'
Rhodium-Catalyzed Reaction Mechanism

31. Rhodium in Wilkinson’s Catalyst (WC)
Rh
Ph 3P PPh 3
PPh 3Cl
Chlorotris(triphenylphosphine)rhodium(I)
The most common catalyst

Wilkinson’s Catalyst, [RhCl(PPh3)3]

32. Geoffrey Wilkinson
Sir Geoffrey Wilkinson FRS,
Professor of Inorganic Chemistry,
Imperial College, London (1956-1988)
Nobel Prize for Chemistry, 1973
Nobel Prize for Rhodium Metal …

33. Robert H. Grubbs
Ruthenium-Catalyzed Reactions

34. Different Ruthenium Catalyst …….

35.  Less reactivity; greater selectivity for
less bulky and or strained alkenes
 Bench stable
 Higher substrate functional group tolerance
Grubbs Catalyst(s)

36. Ruthenium-Catalyzed Olefin Metathesis Reactions

38. Robert H. Grubbs
The Nobel Prize in Chemistry 2005 was awarded jointly to
Yves Chauvin, Robert H. Grubbs and Richard R. Schrock
for the development of the metathesis method in organic synthesis.
Yves Chauvin Richard R. Schrock
Nobel Prize for Ruthenium Metal …

39. Palladium-Catalyzed Coupling Reactions
Useful properties of Palladium:
Relatively inert
Usually has high yield and selectivity
Less expensive than Platinum, which has similar
properties

40. Palladium-Catalyzed Heck Reaction

41. Palladium-Catalyzed Heck Reaction …….

42. Mechanism of the Heck Coupling Reaction

43. Application of Heck Reaction: Natural Products
Isolation: bark of the Pacific yew tree Taxus brevifolia (1967)
-concentration of paclitaxel 0.000008% w/w (10 g/1.2 t of bark)
Bioactivity: antitumor effect against ovarian, lung and breast cancer
-paclitaxel hyperstabilises microtubules and terminates cell division
Production: Taxus cell line fermentation technology
(Phyton Biotech Inc.)
Paclitaxel (Taxol®)

44. Synthetic application of Heck cross-coupling
Paclitaxel (Taxol®)

45. Palladium-Catalyzed Negishi Reaction
R X R' Zn X
catalyst
R'R

46. Mechanism of Negishi Reaction

47. Isolation: Panamaniam poison frog Dendrobates pumilio (1967)
Bioactivity: lipophilic, highly toxic and powerful cardiotonic agent
- efficient skin deterrent and defensive alkaloid against predators
- used as a dart poison by native Indians in Central and South
America
Application of Negishi Reaction : Natural Products
Pumiliotoxin A

48. Synthetic application of Negishi coupling
Pumiliotoxin A

49. Palladium-Catalyzed Suzuki Reaction

50. Mechanism of the Suzuki Coupling Reaction

51. Isolation: Caribbean deep-sea sponge Discodermia dissoluta (1990)
- concentration of discodermolide 0.002% w/w (7 mg/434 g sponge)
-light sensitive compound, sponge must be harvested below 33 m...
Bioactivity: antifungal, immunosuppresive and cytotoxic (IC50= 3-80 nM)
- mode of action resembles that of taxol, i.e. stabilisation of microtubules
- since 2004 in Phase I. clinical trials as potential anticancer agent (Novartis)
Application of Suzuki Reaction : Natural Products
(+)-Discodermolide

52. The Nobel Prize in Chemistry 2010 was awarded jointly to
Richard F. Heck, Ei-ichi Negishi and Akira
Suzuki “for the development of palladium-catalyzed cross
couplings in organic synthesis”
Nobel prize for noble metal Palladium

53. Advance Metal catalyzed
reaction

54. Sonogashira Coupling

55. Mechanism of Sonogashira Coupling

56. Stille Coupling Reaction

57. Mechanism of Stille Coupling Reaction

58. The Wacker-Tsuji Oxidation

59. Karl Barry Sharpless
Titanium(Ti) Catalyzed Reaction

60. Sharpless Epoxidation

61. Sharpless Epoxidation …

62. Nobel Prize in Chemistry (2001)
Karl Barry Sharpless
Hydrogenation and oxidation
Nobel prize for metal Titanium

63.  Metal undergoes oxidative addition
 One alkyl substituent and a nucleophile bind to the
metal catalyst.
 Second substituent also binds/ coordinates to the metal
complex
 Occurs through transmetallation or nucleophilic
attack
 Metal complex undergoes reductive elimination
 Forms a new compound that combines the two
substituents.
Reforms the catalyst
Metal-Catalyzed Cross-Coupling
Reactions

64. THANK YOU