synthesis and characterization of inorganic complexes...

Synthesis andSynthesis and characterization of inorganiccharacterization of inorganic

complexesp

Direct Synthesis methodsDirect Synthesis methods

SY

NTHH

ESISA

ND

Direct synthesis of coordination and organomtallic compounds

DC

HA

RA

Corganomtallic compounds CTER

IZAT

Alexander D Garnovskii

TION

OF

Alexander D. GarnovskiiBoris I. Kharisov

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3

PLEXES 93-92نيم سال اول

SY

NTHH

ESISA

ND

"direct synthesis" of metal complexes starting from metalvapors in the gas phase. D

CH

AR

ACDirect methods: C

TERIZA

T

Direct methods:

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1 Cryosynthesis of metal complexes2 Direct electrosynthesis of metal complexes3 O id ti di l ti f t l d t l id i IN

OR

GA

N

3 Oxidative dissolution of metals and metal oxides in aliquid phase4 Mechanosynthesis of coordination compounds N

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4 Mechanosynthesis of coordination compounds

4


SY

NTHH

ESISA

ND

C h i f l l

DC

HA

RA

C

Cryosynthesis of metal complexes

CTER

IZATTIO

NO

FIN

OR

GA

NNIC

CO

MP

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SY

NTHH

ESISA

ND

A gaseous atom of any element except the noble gases may be expected to be more reactive than the normal form of the l f

DC

HA

RA

C

element for two reasons.

CTER

IZATTIO

NO

F

A) the atom can react faster because it has minimal stericrequirements and generally has readily available electrons or

bi l INO

RG

AN

orbitals.

B) the atom is a species of higher energy than the normal state NIC

CO

MP

B) the atom is a species of higher energy than the normal state of the element (for the heats of formation of the elements

6



SY

NTHH

ESISA

ND

This method limitation is the instability of complexes at high temperatures.

DC

HA

RA

CTemperature rang: usually 10 to 273 K CTER

IZAT

e pe u e g: usu y o 7

condensed TION

OF

Metal (solid) Metal (gas)2000‐2500 K

vacuum

INO

RG

AN

Metal (solid) Metal (gas)

LigandReaction

NIC

CO

MP

glow temperature

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SY

NTH

V i ti th dH

ESISA

ND

Vaporization methods:

resistive heating DC

HA

RA

C

resistive heatinginduction heatingbombardment with electrons of a few Kilovolts C

TERIZA

T

cathodic sputteringlaser irradiation.

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SY

NTHH

ESISA

NDD

CH

AR

ACC

TERIZA

TTION

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NTHH

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ND

electron beam vaporizationD

CH

AR

ACC

TERIZA

TTION

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NTHH

ESISA

ND

laser vaporizationD

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AR

ACC

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solution metal atom reactorS

YN

THsolution metal-atom reactor

HESIS

AN

DDC

HA

RA

CCTER

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NO

FIN

OR

GA

NNIC

CO

MP

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SY

NTHH

ESISA

ND

Transformations in this method:D

CH

AR

AC

σ- and π-coordination of metal atomsInsertion of metals into a C-X bond (X = H, Hal) C

TERIZA

T

se o o e s o C bo d ( , )

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Synthesis of metal complexes with simple inorganic ligandsD

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ND

It is necessary to mention that the well-known nickel tetracarbonyl, obtained more than 100 years ago by the reaction between the bulk metal and CO can also be synthesized by the D

CH

AR

AC

between the bulk metal and CO, can also be synthesized by the unusual direct interaction between nickel vapor and CO2 (as well as with CO) in a yield of--~10% C

TERIZA

T

s w CO) y e d o %

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Cryosynthesis of metal σ- and π-complexesD

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AC

Interaction of metals with olefins Interaction of metals with polyenes C

TERIZA

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Interaction of metals with arenes and hetarenesInteraction of metals with alkynesI t ti f t l ith th li d TIO

NO

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Interaction of metals with other ligandsInteraction of metal with polymers

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NTHCryosynthesis of metal σ- and π-complexes H

ESISA

ND

Interaction o f metals with olefins

Cryosynthesis of metal σ and π complexesD

CH

AR

ACC

TERIZA

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ESISA

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Interaction of metals with polyenesCryosynthesis of metal σ and π complexes

DC

HA

RA

CCTER

IZATTIO

NO

FIN

OR

GA

NNIC

CO

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SY

NTH

Cryosynthesis of metal σ and π complexesH

ESISA

ND

Interaction o f metals with arenes and hetarenesCryosynthesis of metal σ- and π-complexes

DC

HA

RA

CCTER

IZATTIO

NO

FIN

OR

GA

NNIC

CO

MP

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ESISA

ND

Interaction o f metals with alkynesCryosynthesis of metal σ and π complexes

DC

HA

RA

CCTER

IZATTIO

NO

FIN

OR

GA

NNIC

CO

MP

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ESISA

ND

Interaction of metals with other ligandsCryosynthesis of metal σ and π complexes

DC

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C

Complexes obtained from atomic metals and oxygen-containing ligands C

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ESISA

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Interaction of metals with polymersCryosynthesis of metal σ and π complexes

DC

HA

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CCTER

IZATTIO

NO

FIN

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GA

NNIC

CO

MP

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SY

NTH

V th i f t l h l tH

ESISA

ND

Vapor synthesis of metal chelates

The cryosyntheses of metal acetylacetonates with the general DC

HA

RA

C

y y y gformula M(acac)2, where M= Mn, Cr, Fe, Ni, Pd, Cu, Zn, Sn, Pb, and M(acac)3, where M = A1, Cr, Fe, Dy, Ho, Er,

CTER

IZATTIO

NO

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NNIC

CO

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SY

NTHH

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NDDirect methods: D

CH

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AC1 Cryosynthesis of metal complexes C

TERIZA

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1 Cryosynthesis of metal complexes2 Direct electrosynthesis of metal complexes3 Oxidative dissolution of metals and metal oxides in a TIO

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liquid phase4 Mechanosynthesis of coordination compounds

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Direct Electrosynthesis of Metal Complexes

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Direct electrosynthesis of metal complexes

The oldest method DC

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C

The oldest methodSynthesis complex from zero-valent metals.

CTER

IZAT

Gerdes (1882) → platinum(IV) hexaaminates

TION

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(anodic dissolution of a platinum electrode in a solution of ammonium carbonate)

Ch (1908) Th i d f l h i i di i h i INO

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Chugaev (1908) → The systematic study of electrosynthesis in coordination chemistry([C0(NH3)6]C13 [Co(NH3)4C1]SO4 [Co(NH3)4(NO2)2]NO3)cobalt anode and a platinum cathode; N

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Practical aspectsElectrosynthesis is the optimal method for carrying out redoxreactions because it works at normal temperature D

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AC

reactions, because it works at normal temperature.

CTER

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Advantages:- The addition of redox species to the reaction mixture is TIO

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unnecessary.- Compounds are produced by metal dissolution in soft conditions and with very simple equipment independently of IN

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N

conditions and with very simple equipment, independently of the metal being anode or cathode.- It is possible to produce compounds which are very difficult N

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p p p yto obtain by the classical route, especially those with the lowest metal oxidation state. This product selectivity, especially in

i l h i d h f26


organic electrosynthesis, demonstrates the power of electrochemistry.

The electrosynthesized compounds are sometimes more


SY

NTHH

ESISA

ND

Advantages:- The electrosynthesized compounds are sometimes more D

CH

AR

AC

reactive than those obtained by conventional methods.- The working conditions required to obtain the electrodicreactions permit minimum contamination as a consequence of C

TERIZA

T

reactions permit minimum contamination as a consequence of the low amounts of gases liberated, and avoid the danger of explosion during the electrolytic process. Frequently, the TIO

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p g y p q y,electrochemical methods are carried out under milder conditions and at lower temperatures, leading to fewer reaction b d

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byproducts.-At present prices of metals are lower than those of their compounds N

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compounds.

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Advantages:- The use of a metallic salt to produce a coordination compound i li th f i f i th lt Wh th

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C

implies the presence of anion forming the salt. When the process is carried out in the conventional way (from metal salts MX and organic ligands HL), it is possible to obtain the C

TERIZA

T

MX and organic ligands HL), it is possible to obtain the complexes MLX instead of desirable product MLn. The salt anion can participate in the formation of undesirable products. TIO

NO

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- the electrolytical method makes it possible to obtain compounds with a higher metal oxidation state whenever the substitution of the sacrificial anode by a platinum electrode is IN

OR

GA

N

substitution of the sacrificial anode by a platinum electrode is possible.

NIC

CO

MP

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SY

NTHH

ESISA

ND

The application of direct electrosynthesis at an industrial level requires consideration of many factors: D

CH

AR

ACC

TERIZA

T

The availability and price of the starting material.The quantity of product obtained . TIO

NO

F

q y pThe type and quantity of secondary products The price of the product isolated from the electrolytic medium.

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The maximum cell currentThe chemical and electrochemical stability of the electrolytic medium N

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medium.The cell price

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NTH

Experimental parameters:H

ESISA

ND

Experimental parameters:

-The electrode potential. DC

HA

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C

p-The electrode material.-The solvent and supporting electrolyte.

h i f h l i i

CTER

IZAT

-The concentration of the electroactive species.-The pH and concentration of all species that can react with the intermediates TIO

NO

F

intermediates.-The temperature and pressure.-The mass-transport regime, which influences the maximum IN

OR

GA

N

p g ,current density, the intermediate product velocities and the amount of the mixture between the reaction layer and the bulk

l i Th i i d i d b h

NIC

CO

MP

solution. The masstransport regime is determined by the electrolytic flow velocity and the movement of the electrodes.-The geometrical form of the electrodes and the presence or

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-The geometrical form of the electrodes and the presence or absence of separators or membranes.


SY

NTH

Solvent and supporting electrolyteH

ESISA

ND

Solvent and supporting electrolyte

Important points to select solvent: DC

HA

RA

C

p p

-The solubility of the electroactive species and supporting CTER

IZAT

electrolyte.- Poor (or no) reactivity to the products.

Facility of purification TION

OF

- Facility of purification.- Stability to the applied potential gradient of approximately 20 V cm-1. IN

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N

- Dielectric constant values.- Low viscosity (especially if fast transport to electrodes is N

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necessary).- Adequate volatility to facilitate its elimination.

Easy separation by precipitation of the product from the

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- Easy separation by precipitation of the product from the solvent.


SY

NTH

d d lH

ESISA

ND

standard solvents:

alcohols DC

HA

RA

C

alcoholstetrahydrofuran (THF)dimethylformamide (DMF) C

TERIZA

T

y ( )dimethyl sulfoxide (DMSO)acetonitrile (AN)

idi (P ) TION

OF

pyridine (Py)

INO

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AN

such exotic solvents aspropylene carbonate N

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sulfolanediglymeh th l h h t i id

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hexamethylphosphortriamide


SY

NTHH

ESISA

ND

Types of cells

DC

HA

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CCTER

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Undivided cell and divided cell Undivided cells have less resistance than divided ones

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SY

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NDD

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ACC

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SY

NTHH

ESISA

NDD

CH

AR

ACElectrolytic parameters C

TERIZA

T

y p

Using a current range of 20-50 mA TION

OF

The voltage required to obtain this current typicallyranges from 10 to 50 VThe electrosynthesis of coordination compounds is carried out IN

OR

GA

N

The electrosynthesis of coordination compounds is carried out by using a sacrificial anode or cathode

NIC

CO

MP

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SY

NTH

iH

ESISA

ND

Reactions:

DC

HA

RA

CCTER

IZAT

Reactions under solvation conditions

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If ligands (LH) with an acidic EH group (E = NR, O, S, Se) take part in the process of electrosynthesis N

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part in the process of electrosynthesis

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SY

NTHH

ESISA

NDD

CH

AR

AC

l h i ifi i l d

CTER

IZAT

Electrosynthesis at sacrificial anodes

Electrosynthesis of molecular complexes (adducts) TION

OF

Electrosynthesis of molecular complexes (adducts)Electrosynthesis of metal chelatesElectrosynthesis of di- and polymetallic complexes IN

OR

GA

N

y p y pElectrosynthesis of σ- and π-organometallic complexes

El h i ifi i l h d

NIC

CO

MP

Electrosynthesis at sacrificial cathodes

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SY

NTHH

ESISA

ND

Electrosynthesis at sacrificial anodes Electrosynthesis of molecular complexes (adducts)

DC

HA

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CCTER

IZATTIO

NO

FIN

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GA

NNIC

CO

MP

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SY

NTHH

ESISA

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Electrosynthesis at sacrificial anodes Electrosynthesis of molecular complexes (adducts)

DC

HA

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CCTER

IZATTIO

NO

FIN

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GA

NNIC

CO

MP

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SY

NTHH

ESISA

NDD

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SY

NTHH

ESISA

NDElectrosynthesis at sacrificial anodes D

CH

AR

ACElectros nthesis of metal chelates C

TERIZA

T

Electrosynthesis of metal chelates

some chelate-forming ligands, such as dimethylglyoxime, TION

OF

some chelate forming ligands, such as dimethylglyoxime, β-diketones, azomethines, oxyphenylazoles, …

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SY

NTHH

ESISA

NDD

CH

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ACC

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TTION

OF

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SY

NTHH

ESISA

NDD

CH

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ACC

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OF

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ESISA

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Electrosynthesis at sacrificial anodes Electrosynthesis of di- and polymetallic complexes

DC

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CFew publications CTER

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Few publications The cadmium complex of composition CdL2

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ESISA

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Electrosynthesis at sacrificial anodes Electrosynthesis of σ- and π-organometallic complexes D

CH

AR

ACC

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TTION

OF

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SY

NTHH

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NDD

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ESISA

ND

What is the advantage and disadvantage of this cryo method:

Formation o very low temperature stable compound DC

HA

RA

C

Formation o very low temperature stable compound

CTER

IZAT

Rigidity of matrixHard and expensive technique TIO

NO

FIN

OR

GA

NNIC

CO

MP

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SY

NTHH

ESISA

ND

Note: There is a difference between this metal-vapor/cryosynthesis method and other types of "direct

h i " [27] (i id i di l i f b lk l

DC

HA

RA

C

synthesis" [27] (i.e. oxidative dissolution of bulk metals, electro- and mechanosynthesis). Thus, in this case, the bulk metal must be vaporized before its reaction with gaseous or C

TERIZA

T

metal must be vaporized before its reaction with gaseous or frozen (in)organic ligand. This step is necessary to provide the absence for the metal of the kinetic or thermodynamic barriers TIO

NO

F

ythat exist for the bulk metals, and this is precisely the reason for the success of cryosynthesis.

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synthesis and characterization of inorganic complexes...

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