traditional aqueous routes - is.muni.cz elimination ester elimination alkene elimination acetamide...

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Traditional Aqueous Routes Advantages Simple Equipment Inexpensive Materials Well Studied Disadvantages Difficult control of hydrolysis and condensation rates Inhomogeneity introduced by homocondensation Reversibility of condensation step Phase Separation M-O-M' + H-O-H M-OH + HO-M' 2 M-OH + 2 HO-M' M-O-M + M'-O-M' + 2 HOH

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Page 1: Traditional Aqueous Routes - is.muni.cz Elimination Ester Elimination Alkene Elimination Acetamide Elimination Ether Elimination Ketene Elimination Ketimine Elimination

Traditional Aqueous RoutesAdvantages

Simple EquipmentInexpensive MaterialsWell Studied

Disadvantages

Difficult control of hydrolysis and condensation ratesInhomogeneity introduced by homocondensationReversibility of condensation stepPhase Separation

M-O-M' + H-O-H M-OH + HO-M'

2 M-OH + 2 HO-M' M-O-M + M'-O-M' + 2 HOH

Page 2: Traditional Aqueous Routes - is.muni.cz Elimination Ester Elimination Alkene Elimination Acetamide Elimination Ether Elimination Ketene Elimination Ketimine Elimination

Nonaquoeus – Nonhydrolytic –Organometallic Methods

M-O-X + Z-M' X-Z + M-O-M'

Advantages

Inhomogeneity and phase separation prevented absence of water, volatile organic byproducts cannot cleave M-O-M’ bonds and cause homocondensation, irreversible condensation step

M = mononuclear, polynuclear clusters, building blocks

Chemical control of reactivity by selecting X, Z groups

Wide choice of solvents, medium polarity, reaction temperature

Simplified drying to aerogels, lower surface tension

Page 3: Traditional Aqueous Routes - is.muni.cz Elimination Ester Elimination Alkene Elimination Acetamide Elimination Ether Elimination Ketene Elimination Ketimine Elimination

Nonaquoeus – Nonhydrolytic –Organometallic Methods

Advantages

Synthesis of hybrid materials incorporation of water sensitive and water insoluble compounds: organometallics, coordination compounds, long aliphatic chains, clustershydrophobic hybrid materials

Template synthesesuse of water sensitive and water insoluble compounds, polymersmicroporous and mesoporous

Retention of lower coordination numbers (Al, TM), low-hydroxyl surfaces – catalysis

Page 4: Traditional Aqueous Routes - is.muni.cz Elimination Ester Elimination Alkene Elimination Acetamide Elimination Ether Elimination Ketene Elimination Ketimine Elimination

Nonaquoeus – Nonhydrolytic –Organometallic Methods

Disadvantages

- Elaborate procedures and expensive precursors

- Organic solvents

- Exclusion of moisture

- Ligand scrambling vs. elimination

Page 5: Traditional Aqueous Routes - is.muni.cz Elimination Ester Elimination Alkene Elimination Acetamide Elimination Ether Elimination Ketene Elimination Ketimine Elimination

Nonaquoeus – Nonhydrolytic –Organometallic Methods

Solid-state: solid-state thermolysis

Liquid-state: sol-gel, solventless, sonochemical reactions,

solution thermolysis

Gas-phase: CVD, pyrosol

Page 6: Traditional Aqueous Routes - is.muni.cz Elimination Ester Elimination Alkene Elimination Acetamide Elimination Ether Elimination Ketene Elimination Ketimine Elimination

Preparation of Oxides, Mixed Oxides, and Silicates

Alkylhalide Elimination

Ester Elimination

Alkene Elimination

Acetamide Elimination

Ether Elimination

Ketene Elimination

Ketimine Elimination

Page 7: Traditional Aqueous Routes - is.muni.cz Elimination Ester Elimination Alkene Elimination Acetamide Elimination Ether Elimination Ketene Elimination Ketimine Elimination

Alkylhalide Elimination ReactionsM = Si, Al, Ti, Zr, V, Nb, Mo, W, Fe

M-X + R-O-M' M-O-M' + R-X

M-O-M' + R-X

M-O-R + HX

M-X + R-O-R M-O-R + R-X

M-O-R + X-M'

M-X + H-O-R

M-O-R + X-M'

M-O-M' + R-X

Corriu, Vioux, Leclercq, Mutin, MontpellierHay et al., Surrey

Page 8: Traditional Aqueous Routes - is.muni.cz Elimination Ester Elimination Alkene Elimination Acetamide Elimination Ether Elimination Ketene Elimination Ketimine Elimination

Alkylhalide Elimination Reactions

MRO

OR

ROO M

O

RO OROR

MX

XX

- RXMX

X

X X

R MRO

OR

RO O

MX X

X X

R

C-O bond cleavage

Page 9: Traditional Aqueous Routes - is.muni.cz Elimination Ester Elimination Alkene Elimination Acetamide Elimination Ether Elimination Ketene Elimination Ketimine Elimination

MRO

OR

RO O

MX X

X X

R

MRO

OR

RO O

MX

X

XX

R

MRO

OR

RO O

MXX

X X

R

MRO

OR

RO O

MX X

X X

R

M

O

RO OROR

MX

XX

- RX

- RX

- RX

Page 10: Traditional Aqueous Routes - is.muni.cz Elimination Ester Elimination Alkene Elimination Acetamide Elimination Ether Elimination Ketene Elimination Ketimine Elimination

Alkylhalide Elimination Reactions

TiCl4 + Ti(OR)4 + TOPO

heptadecane 300 °C

TiO2 anatase10 nm

+ RClR = Me, Et, i-Pr, t-Bu

Colvin et al., J. Am. Chem. Soc., 1999, 121, 1613

Page 11: Traditional Aqueous Routes - is.muni.cz Elimination Ester Elimination Alkene Elimination Acetamide Elimination Ether Elimination Ketene Elimination Ketimine Elimination

Alkylhalide Elimination Reactions

AlCl3 + Si(OEt)4 + Et2O

CCl4, 110 °C

Al-O-Si gel

900 °C

3Al2O3. 2SiO2

mulliteJanackovic et al., NanoStructured Materials, 1999, 12, 147

Page 12: Traditional Aqueous Routes - is.muni.cz Elimination Ester Elimination Alkene Elimination Acetamide Elimination Ether Elimination Ketene Elimination Ketimine Elimination

Alkylhalide Elimination Reactions

H3C C

O

O Et

Cl

TiCl Cl

Cl AP-CVD 400 - 600 °C+ TiO2 anatase

Parkin I. et al., Chem. Mater., 2003, 15, 46

Page 13: Traditional Aqueous Routes - is.muni.cz Elimination Ester Elimination Alkene Elimination Acetamide Elimination Ether Elimination Ketene Elimination Ketimine Elimination

Ester Elimination Reactions: acetates + alkoxides

M = Zr, Si, Ti, Ba, Sn, Pb

SiO

O

R

MO

R'

MO

Si

O

O

RR'

++

Jansen, Guenther, Chem. Mater., 1995, 7, 2110

Hampden-Smith et al., Chem. Comm., 1995, 157

Page 14: Traditional Aqueous Routes - is.muni.cz Elimination Ester Elimination Alkene Elimination Acetamide Elimination Ether Elimination Ketene Elimination Ketimine Elimination

Ester Elimination Reactions: alkoxides + acid anhydrides

O

O

R'

O

MRO

OR

OROR

M'O

O

O

OM

O

O

O

O

O

R'R

R'

2 1/2

2

++

M = Si, M' = Ti

Fujiwara et al., Chem. Mater., 2002, 14, 4975

Page 15: Traditional Aqueous Routes - is.muni.cz Elimination Ester Elimination Alkene Elimination Acetamide Elimination Ether Elimination Ketene Elimination Ketimine Elimination

Ester Elimination Reactions: alkoxides + acid anhydrides

SiRO

OR

OROR

BO

O

OSi

O

O

O

O

BO

B

OB

RO OR

OR

ROB

OR

OR

R = Me, Et

+

+

acetone gel

600 °C

borosilicate glassBecket et al., Chem. Comm., 2000, 1499

Page 16: Traditional Aqueous Routes - is.muni.cz Elimination Ester Elimination Alkene Elimination Acetamide Elimination Ether Elimination Ketene Elimination Ketimine Elimination

Ester Elimination Reactions

Ti(NO3)4 + Si(OEt)4 SiO2/TiO2 + 4 EtONO2

CVD , 300 - 535 °C

Gladfelter et al., Chem. Mater., 2000, 12, 2822

Page 17: Traditional Aqueous Routes - is.muni.cz Elimination Ester Elimination Alkene Elimination Acetamide Elimination Ether Elimination Ketene Elimination Ketimine Elimination

Alkene Elimination: tris(tert-butoxy)silanolates

SiO

O

O

OM

O

O

O

SiO

O

OOM M

Si

SiSi

Si

Si +

M = Ti, Zr, Hf, Al, Cr, Cu, Zn, Mo, W, V

Tilley et al., Berkely

Page 18: Traditional Aqueous Routes - is.muni.cz Elimination Ester Elimination Alkene Elimination Acetamide Elimination Ether Elimination Ketene Elimination Ketimine Elimination

Alkene Elimination: tris(tert-butoxy)silanolates

SiO

O

O

OM

CH3

CH3

H

HH

SiO

O

O

OHM

H3C CH3

H H

+

β-Hydrogen Elimination

Page 19: Traditional Aqueous Routes - is.muni.cz Elimination Ester Elimination Alkene Elimination Acetamide Elimination Ether Elimination Ketene Elimination Ketimine Elimination

Acetamide Elimination

Si

O

O OO

MO

OO

Si

AcO

AcO

AcO

O

O

CH3

AlMe2N

Me2N

Me2NNMe2

O

CH3Me2N

++

AlNMe2

NMe2

gel

950 °C

3Al2O3.2SiO2mullite

Pinkas J., Lobl J., Roesky H. W. unpublished

Page 20: Traditional Aqueous Routes - is.muni.cz Elimination Ester Elimination Alkene Elimination Acetamide Elimination Ether Elimination Ketene Elimination Ketimine Elimination

Ether Elimination

SiO

R

RRM M'

OM

RO

M'

++Si

O

R

RRR

Hampden-Smith et al.,

Page 21: Traditional Aqueous Routes - is.muni.cz Elimination Ester Elimination Alkene Elimination Acetamide Elimination Ether Elimination Ketene Elimination Ketimine Elimination

Ketene Elimination

+

H

OAl

R

O

O

H

Et

Bu

OHAl

R

OH

Bu

C

Et

C O

))))), 10 min

decanegel

γ-Al2O3 (10 nm)

Y3Al5O12

LaAlO3

700 - 900 °C

CN(Al) = 6

Ulman et al., J. Am. Chem. Soc., 2003, 125, 4010

Page 22: Traditional Aqueous Routes - is.muni.cz Elimination Ester Elimination Alkene Elimination Acetamide Elimination Ether Elimination Ketene Elimination Ketimine Elimination

Ketimine Elimination

Lindquist et al., Chem. Mater., 2003, 15, 51

H2N

AlNH2

Al

NH2

Al

Et Et

Et

Et

Et

Et O+

NH+ +EtH EtAlO

H2O

AlO(OH) high porosity

- EtH

Page 23: Traditional Aqueous Routes - is.muni.cz Elimination Ester Elimination Alkene Elimination Acetamide Elimination Ether Elimination Ketene Elimination Ketimine Elimination

Thermolysis of a single-source precursor

Ti

O

R2N

i-PrO

i-PrO

i-PrO TOPO 325 °CTiO2 anatase3 nm

Fischer et al., J. Mater. Chem. 2002, 12, 1625

Page 24: Traditional Aqueous Routes - is.muni.cz Elimination Ester Elimination Alkene Elimination Acetamide Elimination Ether Elimination Ketene Elimination Ketimine Elimination

Preparation of Phosphates and Phosphonates

Alkane/Hydrogen Elimination

Alkene Elimination

Alkylhalide Elimination

Alkylsilane Elimination

Aklylamine Elimination

Alcohol Elimination

Ether Elimination

Chlororsilane Elimination

Diketone/Ester Route

Page 25: Traditional Aqueous Routes - is.muni.cz Elimination Ester Elimination Alkene Elimination Acetamide Elimination Ether Elimination Ketene Elimination Ketimine Elimination

Alkane/Hydrogen Elimination

PO

OH

ROH

AlO

F

OP

O

OR

n

R = Me, Ph, n-Oct, n-Dodec

EtH+

AlO

Cl

OP

O

OR

nMe2Zn

H2AlCl(THF)2

+ H2

2 MeH+(RPO3)Zn

R = Me, Ph, thienyl, Me-thiophenyllayered

Et2AlF

Gerbier et al., J. Mater. Chem. 1999, 9, 2559

Knight et al., J. Organometal. Chem. 1999, 585, 162

Schmidt et al., J. Polym. Sci. A, 1968, 6, 3235

Page 26: Traditional Aqueous Routes - is.muni.cz Elimination Ester Elimination Alkene Elimination Acetamide Elimination Ether Elimination Ketene Elimination Ketimine Elimination

Alkene Elimination

PO

Al

OP

O

Al

O

X

X X

X

OO

O O X = Me, OiPr

AlPO4 + XH +

Tilley et al., J. Am. Chem. Soc. 2001, 123, 10133

X = Si(OtBu)3Al2P2Si3O14

Page 27: Traditional Aqueous Routes - is.muni.cz Elimination Ester Elimination Alkene Elimination Acetamide Elimination Ether Elimination Ketene Elimination Ketimine Elimination

Alkene Elimination: tris(tert-butoxy)silanolates

P

O

Al

O Al

O

PO

OAl O P

O

O

AlO

OP

O

O

O

Si

OtBu

OtBuButO

OSi

OtBuOtBu

OtBu

OSiButO

ButO

ButO

P

OAl

OAl

O

P

OO

Al

O

PO

O

Al

O

O

POO

P

O

Al

O Al

O

PO

OAl O P

O

O

AlO

OP

O

O

P O Al

O

Al O P

O

OAl

O

PO O Al

O

OPH

O

O

O

O

O

O

O

O

O

SiO2SiO2

O

SiO2

- H2O- isobutene

O

Pinkas J., Brlejova Z., Roesky H. W. unpublished

Page 28: Traditional Aqueous Routes - is.muni.cz Elimination Ester Elimination Alkene Elimination Acetamide Elimination Ether Elimination Ketene Elimination Ketimine Elimination

Alkene Elimination: tris(tert-butoxy)silanolates

isobutene + H2O

Page 29: Traditional Aqueous Routes - is.muni.cz Elimination Ester Elimination Alkene Elimination Acetamide Elimination Ether Elimination Ketene Elimination Ketimine Elimination

Alkylhalide EliminationNonhydrolytic synthesis of NASICONNa3Zr2Si2PO12 solid electrolyte, high Na+ ionic conductivity

- Solid state preparation: dissolved ZrO2

- Sol-gel from alkoxides: very slow hydrolysis necessary, different hydrolysis rates

- Nonhydrolytic route in CH3CN

OP(OnBu)3 + SiCl4 + Zr(OtBu)4 + NaOtBu → nBuCl + tBuCl +

Gel formationSolvent and byproduct evaporation under vacuumDrying at 120 °C for 15 hBall millingCalcination at 800 °C gives NASICON

O P O Si O Zr OO

O O

OCl

ClBu

Bu tBu

tBu

tBu

Di Vona et al., J. Sol-Gel Sci. Technol., 2000, 1/3, 463

Page 30: Traditional Aqueous Routes - is.muni.cz Elimination Ester Elimination Alkene Elimination Acetamide Elimination Ether Elimination Ketene Elimination Ketimine Elimination

Ether Elimination

O

AlO

P O

P

O

AlMe

Me

Me

Me

O

OMe3Si

SiMe3

O

O

Me3Si

SiMe3

O

AlO

P O

P

O

AlMe

Me

Me

Me

OH

HO

OH

OHCF3CH2OH

- CF3CH2OSiMe3

CH3-AlPO4 gelPinkas J., Moravec, Z., Roesky H. W. unpublished

Page 31: Traditional Aqueous Routes - is.muni.cz Elimination Ester Elimination Alkene Elimination Acetamide Elimination Ether Elimination Ketene Elimination Ketimine Elimination

Chlororsilane Elimination

AlCl3 + OP(OSiMe3)3THF, reflux

AlPO4 tridymite13% Si

gel AlPO4+ ClSiMe3

800 °C

Pinkas J., et al. Inorg. Chem. 1998, 37, 2450

Page 32: Traditional Aqueous Routes - is.muni.cz Elimination Ester Elimination Alkene Elimination Acetamide Elimination Ether Elimination Ketene Elimination Ketimine Elimination

Diketone/Ester Route

Daviero et al., J. Non-Cryst. Solids, 1992, 146, 279, Thin Solid Films, 1993, 226, 207

O

AlO

O O

O

O

O P

OR

OROR

+

pyrosol CVD processin ethanol, 300 – 400 °C

AlPO4 amorphous