Metal carbonyls are coordination complexes of transition metals with carbon monoxide ligands. They were first synthesized in 1868 by passing carbon monoxide over platinum. Metal carbonyls typically obey the 18 electron rule and are often diamagnetic. They have applications as catalysts in organic synthesis and in producing pure metals like nickel. Precautions must be taken when using metal carbonyls due to their toxicity.
Classification Of Mechanisms, Ligand Substitution In Octahedral Complexes Without Breaking Metal-ligand Bond, Substitution Reaction In Square Planar Complexes, Factors Which Affect The Rate Of Substitution, Trans Effect (Labilizing Effect), Theories and applications Of Trans Effect
Classification Of Mechanisms, Ligand Substitution In Octahedral Complexes Without Breaking Metal-ligand Bond, Substitution Reaction In Square Planar Complexes, Factors Which Affect The Rate Of Substitution, Trans Effect (Labilizing Effect), Theories and applications Of Trans Effect
This presentation describes about the preparation, properties, bonding modes, classification and applications of metal Dioxygen Complexes. Also explains the MO diagram of molecular oxygen.
Organometallic Reactions and CatalysisRajat Ghalta
Organometallic compounds undergo a rich variety of reactions (oxidative addition, reductive elimination, cyclometalization, migratory insertion, carbonylation, hydrometallation hydrate elimination, etc ) that can sometimes be combined into useful homogeneous catalytic cycles. In this presentation, I have discussed organometallic reactions of particular importance for synthetic and catalytic processes like the oxo process (hydroformylation), heck coupling reaction, Wilkinson’s Catalyst
(Hydrogenation) etc.
These are chemical shift reagents and solvent induced shifts have their application in resolving the NMR Spectra of complex structures by inducing shift with respect to reference compound. Thus useful in interpretation of structures of complex organic compounds.
Crown ethers
NOMENCLATURE
GENERAL SYNTHESIS OF CROWN ETHER
AZA CROWN
CRYPTAND
APPLICATIONS
1. SYNTHETIC APPLICTION
Esterification
Saponification
Anhydride formation
Potassium permanganate oxidation
Aromatic substitution reactions
Elimination reactions
Displacement reaction
Generation of carbenes
Superoxide anion
Alkylations – 1. o-alkylations
2. c-alkylations
3. n-alkylations
2. ANALYTICAL APPLICATION
Determination of gold in geological samples
Super critical fluid extraction of trace metal from solid and liquid materials
Application of ionic liquids in analytical chemistry
Oxidation and determination of aldehydes
Crown ethers are used in the laboratory as phase transfer catalyst
OTHER APPLICATION
It is used in photocynation
Resolution of racemic mixture
Benzoin condensation
Hetrocyclisation
Synthesis of furanones
Acetylation of secondary amines in presence of primary amine
An overview of the use of the Marcus Theory to calculate the energies of transition states.
Contributed by: Elizabeth Greenhalgh, Amanda Bischoff, and Matthew Sigman, University of Utah, 2015
The homolytic cleavage of covalent bonds in carbonyl compound under photochemical conditions known as Norrish Type Reactions
They are divided into two types
Norrish Type I
Norrish Type II reaction
A ppt compiled by Yaseen Aziz Wani pursuing M.Sc Chemistry at University of Kashmir, J&K, India and Naveed Bashir Dar, a student of electrical engg. at NIT Srinagar.
Warm regards to Munnazir Bashir also for providing us with refreshing tea while we were compiling ppt.
This presentation describes about the preparation, properties, bonding modes, classification and applications of metal Dioxygen Complexes. Also explains the MO diagram of molecular oxygen.
Organometallic Reactions and CatalysisRajat Ghalta
Organometallic compounds undergo a rich variety of reactions (oxidative addition, reductive elimination, cyclometalization, migratory insertion, carbonylation, hydrometallation hydrate elimination, etc ) that can sometimes be combined into useful homogeneous catalytic cycles. In this presentation, I have discussed organometallic reactions of particular importance for synthetic and catalytic processes like the oxo process (hydroformylation), heck coupling reaction, Wilkinson’s Catalyst
(Hydrogenation) etc.
These are chemical shift reagents and solvent induced shifts have their application in resolving the NMR Spectra of complex structures by inducing shift with respect to reference compound. Thus useful in interpretation of structures of complex organic compounds.
Crown ethers
NOMENCLATURE
GENERAL SYNTHESIS OF CROWN ETHER
AZA CROWN
CRYPTAND
APPLICATIONS
1. SYNTHETIC APPLICTION
Esterification
Saponification
Anhydride formation
Potassium permanganate oxidation
Aromatic substitution reactions
Elimination reactions
Displacement reaction
Generation of carbenes
Superoxide anion
Alkylations – 1. o-alkylations
2. c-alkylations
3. n-alkylations
2. ANALYTICAL APPLICATION
Determination of gold in geological samples
Super critical fluid extraction of trace metal from solid and liquid materials
Application of ionic liquids in analytical chemistry
Oxidation and determination of aldehydes
Crown ethers are used in the laboratory as phase transfer catalyst
OTHER APPLICATION
It is used in photocynation
Resolution of racemic mixture
Benzoin condensation
Hetrocyclisation
Synthesis of furanones
Acetylation of secondary amines in presence of primary amine
An overview of the use of the Marcus Theory to calculate the energies of transition states.
Contributed by: Elizabeth Greenhalgh, Amanda Bischoff, and Matthew Sigman, University of Utah, 2015
The homolytic cleavage of covalent bonds in carbonyl compound under photochemical conditions known as Norrish Type Reactions
They are divided into two types
Norrish Type I
Norrish Type II reaction
A ppt compiled by Yaseen Aziz Wani pursuing M.Sc Chemistry at University of Kashmir, J&K, India and Naveed Bashir Dar, a student of electrical engg. at NIT Srinagar.
Warm regards to Munnazir Bashir also for providing us with refreshing tea while we were compiling ppt.
This Presentation describes about the evidence of metal ligand bonding in a molecule. In this presentation various evidences are explained. Learn and grow.
It contains information about various theories of chemical bonding, mainly CFT. It discusses the splitting diagrams of octahedral, tetrahedral and square planar fields. Jahn-Teller distortion is also explained here in simple terms.
Cancer cell metabolism: special Reference to Lactate PathwayAADYARAJPANDEY1
Normal Cell Metabolism:
Cellular respiration describes the series of steps that cells use to break down sugar and other chemicals to get the energy we need to function.
Energy is stored in the bonds of glucose and when glucose is broken down, much of that energy is released.
Cell utilize energy in the form of ATP.
The first step of respiration is called glycolysis. In a series of steps, glycolysis breaks glucose into two smaller molecules - a chemical called pyruvate. A small amount of ATP is formed during this process.
Most healthy cells continue the breakdown in a second process, called the Kreb's cycle. The Kreb's cycle allows cells to “burn” the pyruvates made in glycolysis to get more ATP.
The last step in the breakdown of glucose is called oxidative phosphorylation (Ox-Phos).
It takes place in specialized cell structures called mitochondria. This process produces a large amount of ATP. Importantly, cells need oxygen to complete oxidative phosphorylation.
If a cell completes only glycolysis, only 2 molecules of ATP are made per glucose. However, if the cell completes the entire respiration process (glycolysis - Kreb's - oxidative phosphorylation), about 36 molecules of ATP are created, giving it much more energy to use.
IN CANCER CELL:
Unlike healthy cells that "burn" the entire molecule of sugar to capture a large amount of energy as ATP, cancer cells are wasteful.
Cancer cells only partially break down sugar molecules. They overuse the first step of respiration, glycolysis. They frequently do not complete the second step, oxidative phosphorylation.
This results in only 2 molecules of ATP per each glucose molecule instead of the 36 or so ATPs healthy cells gain. As a result, cancer cells need to use a lot more sugar molecules to get enough energy to survive.
Unlike healthy cells that "burn" the entire molecule of sugar to capture a large amount of energy as ATP, cancer cells are wasteful.
Cancer cells only partially break down sugar molecules. They overuse the first step of respiration, glycolysis. They frequently do not complete the second step, oxidative phosphorylation.
This results in only 2 molecules of ATP per each glucose molecule instead of the 36 or so ATPs healthy cells gain. As a result, cancer cells need to use a lot more sugar molecules to get enough energy to survive.
introduction to WARBERG PHENOMENA:
WARBURG EFFECT Usually, cancer cells are highly glycolytic (glucose addiction) and take up more glucose than do normal cells from outside.
Otto Heinrich Warburg (; 8 October 1883 – 1 August 1970) In 1931 was awarded the Nobel Prize in Physiology for his "discovery of the nature and mode of action of the respiratory enzyme.
WARNBURG EFFECT : cancer cells under aerobic (well-oxygenated) conditions to metabolize glucose to lactate (aerobic glycolysis) is known as the Warburg effect. Warburg made the observation that tumor slices consume glucose and secrete lactate at a higher rate than normal tissues.
Multi-source connectivity as the driver of solar wind variability in the heli...Sérgio Sacani
The ambient solar wind that flls the heliosphere originates from multiple
sources in the solar corona and is highly structured. It is often described
as high-speed, relatively homogeneous, plasma streams from coronal
holes and slow-speed, highly variable, streams whose source regions are
under debate. A key goal of ESA/NASA’s Solar Orbiter mission is to identify
solar wind sources and understand what drives the complexity seen in the
heliosphere. By combining magnetic feld modelling and spectroscopic
techniques with high-resolution observations and measurements, we show
that the solar wind variability detected in situ by Solar Orbiter in March
2022 is driven by spatio-temporal changes in the magnetic connectivity to
multiple sources in the solar atmosphere. The magnetic feld footpoints
connected to the spacecraft moved from the boundaries of a coronal hole
to one active region (12961) and then across to another region (12957). This
is refected in the in situ measurements, which show the transition from fast
to highly Alfvénic then to slow solar wind that is disrupted by the arrival of
a coronal mass ejection. Our results describe solar wind variability at 0.5 au
but are applicable to near-Earth observatories.
This pdf is about the Schizophrenia.
For more details visit on YouTube; @SELF-EXPLANATORY;
https://www.youtube.com/channel/UCAiarMZDNhe1A3Rnpr_WkzA/videos
Thanks...!
THE IMPORTANCE OF MARTIAN ATMOSPHERE SAMPLE RETURN.Sérgio Sacani
The return of a sample of near-surface atmosphere from Mars would facilitate answers to several first-order science questions surrounding the formation and evolution of the planet. One of the important aspects of terrestrial planet formation in general is the role that primary atmospheres played in influencing the chemistry and structure of the planets and their antecedents. Studies of the martian atmosphere can be used to investigate the role of a primary atmosphere in its history. Atmosphere samples would also inform our understanding of the near-surface chemistry of the planet, and ultimately the prospects for life. High-precision isotopic analyses of constituent gases are needed to address these questions, requiring that the analyses are made on returned samples rather than in situ.
3. •Metal carbonyls are coordination complexes of transition metals with carbon
monoxide ligands in low oxidation state. In this ,CO ligands acts as neutral ligands
•Metal carbonyl compounds were first synthesized in by Paul Schützenberger in 1868
by passing chlorine and carbon monoxide over platinum black, where
dicarbonyldichloroplatinum (Pt(CO)2Cl2) was formed.
•Although many compounds were produced, they couldn’t be fully characterized until
the development of X-ray diffraction, and IR and NMR spectroscopy.
•In general, these compounds obey the “18 electron rule.”
•Normally dimagnetics.
•Mononerics are colourless where polymerics are coloured.
•Poor conductors of electricity & Sublimated at low temp
•Soluble in organic solvents.
4.
5. 1. Direct reaction of metal with carbon monoxide
Ni + 4 CO → Ni(CO)4 (1 bar, 55 °C)
Fe + 5 CO → Fe(CO)5 (100 bar, 175 °C)
2. Reduction of metal salts and oxides
CrCl3 + Al + 6 CO → Cr(CO)6 + AlCl3
3. Preparation of dinuclear carbonyls from mononuclear
carbonyls (Photolysis and thermolysis )
Fe(CO)5 → Fe(CO)9+CO
6. 1.CO substitution
M(CO)n → M(CO)n-1 + L → M(CO)n-1L
2.REDUCTIONS
Mn2(CO)10 + 2 Na → 2 Na[Mn(CO)5]
Fe(CO)5 + 2 Na → Na2[Fe(CO)4] + CO
3.Nucleophilic attack at CO
Fe(CO)5 + NaOH → Na[Fe(CO)4CO2H]
4.With electrophiles
Fe(CO)5 + X2 → Fe(CO)4X2 + CO
8. Formation of σ-bond:
The overlapping of empty hybrid orbital on metal atom with the filled hybrid
orbital on carbon atom of carbon monoxide molecule through lone pair
electrons results into the formation of a M←CO σ-bond.
Formation of π-bond by back donation:
This bond is formed because of overlapping of filled dπ orbitals or hybrid dpπ
orbitals of metal atom with antibonding pi orbitals on CO molecule.
9. Bridging CO groups:
In addition to the linear M-C-O groups, the carbon monoxide ligand is also known
to form bridges.
This type of bonding is observed in some binuclear and polynuclear carbonyls.
It is denoted by μn–CO, where n indicates the number of metals bridged. While
n=2 is the most common value, it reaches to be 3 or 4 in certain less common
carbonyls.
In a terminal M-C-O group, the carbon monoxide donates two electrons to an
empty metal orbital, while in μ2–CO group, the M-C bond is formed by sharing of
one metal electron and one carbon electron.
M----M Bond
In some carbonyls another bond develops between metal-metal due to weak
overlap of the two singly filled appropriate hybrid orbitals.
Also called fractional single bond and longer than normal single bond.
12. •The C-O vibration, typically denoted νCO, occurs at 2143 cm−1 for CO gas. The
energies of the νCO band for the metal carbonyls correlates with the strength of the
carbon-oxygen bond, and inversely correlated with the strength of the π-backbonding
between the metal and the carbon.
•The π basicity of the metal center depends on a lot of factors; in the isoelectronic series
(Ti to Fe) at the bottom of this section, the hexacarbonyls show decreasing π-
backbonding as one increases (makes more positive) the charge on the metal. π-Basic
ligands increase π-electron density at the metal, and improved backbonding reduces
νCO. (As the π* orbital on CO receives electrons from the metal, the CO bond weakens
and the ν decreases.)
Compound
[Fe(CO)6]2+ 2204
[Mn(CO)6]+ 2143
Cr(CO)6 2090
[V(CO)6]- 1860
[Ti(CO)6]2- 1750
ν (cm-1)
13. The more symmetrical the structure, the fewer CO stretches
are observed in the IR spectra.
If CO ligands are cis to each
other, both the symmetric stretch
and the asymmetric stretch will
involve a change in dipole
moment, and hence two peaks will
be observed in IR spectra.
If there is a center of
symmetry, with CO ligands trans
to each other, a symmetrical
stretch will not involve a change in
dipole moment, so it will be IR
inactive. An asymmetric stretch
will be seen in the IR spectrum.
As a result, trans carbonyls give
one peak in the IR spectrum.
14. 1. DETERMINATION OF GEOMETRY OF CARBONYLS :-
TBP structure of Fe(CO)5
Calculating no of IR active bands with Raman active bands and then tally with no of
bands predicted theoretically
15. 2. DETERMINATION OF BOND ORDER:-
3. DETERMINATION OF TERMINAL & BRIDGING CARBONYL GROUP:-
16. Ligand.Metal carbonyls are useful in organic synthesis and as catalysts or
catalyst
Precursors in homogeneous catalysis, such as hydroformylation and Reppe
chemistry.
H2 + CO + CH3CH=CH2 → CH3CH2CH2CHO
Dicobalt octacarbonyl acts as catalyst
In the Mond process, nickel carbonyl is used to produce pure nickel.
In organometallic chemistry,metal carbonyls serve as precursors for the
preparation of other ogranometalic complexes.
Metal carbonyls are toxic by skin contact, inhalation or ingestion, in part because
of their ability to carbonylate hemoglobin to give carboxyhemoglobin, which
prevents the binding of O2. That is why precaution is used before using it.
SOME OTHER APPLICATIONS