gaining new vitality: chemistry of monovalent aluminum species

Gaining New Vitality: Chemistry of Monovalent Aluminum Species

Presenter: Tongtong LiuSupervisor: Prof. Zhangjie Shi

Fudan University2020-11-27

1

2

Contents

*

3

Background

Bauxite

Bayer process

Alumina(Al2O3) Aluminium

Electrolysis

H. Yamamoto, K. Oshima, Wiley-VCH, Weinheim, 2004, pp. 189 - 306

Aluminium trihalides (AlX3)

R X

O AlX3R R R

O

CHO

AlCl3CHO

Halogenated Alkylaluminium (AlR3-xXx)

O

OO

ROTBDPS

O

OO

ROTBDPS

HEt2AICI-Ph3P

NNN

Ar Ar

AlCl N

NNAr ArAl

Sandro Gambarotta et al. J. Am. Chem. Soc. 2005, 127, 17204.

4

BackgroundTrialkylaluminiums (AlR3)

A. H. Hoveyda et al. Angew. Chem. Int. Ed. 2008, 47, 7358. S. Xu et al. et al. Chin. J. Org. Chem. 2003, 10, 1049.

Triarylaluminiums (AlAr3)

H. M. Gau et al. Angew. Chem. Int. Ed. 2007, 46, 5373. D. W. Stephan et al. J. Am. Chem. Soc. 2013, 135, 17.

5

Background

Rich oxidation statesOxidation addition Reductive elimination

Cross-CouplingCatalytic HydrogenationOlefin MetathesisOxidation Reaction etc.

6

Background

formal oxidation states

0 +1 +2 +30 +1 +2

1s2 2s2 2p6 3s2 3p1

7

Background


0 +1 +2 +30 +2

1s2 2s2 2p6 3s2 3p1

1s2s3s 3p

2pOxidation addition

σ donor

8

Background


0 +1 +2 +3

Considerably less commonRare catalytic reaction

0 +1 +2

H. Schnöckel et al. Angew. Chem. Int. Ed. Engl. 1991, 30, 564.H. W. Roesky et al. Angew. Chem. Int. Ed. Engl. 2000, 39, 4274.S. Aldridge et al. Nature 2018, 557, 92.

1s2 2s2 2p6 3s2 3p1

9

Contents

*

10

2 Al + Cl2(g)1000 oC

2 AlCl(g)

W. Klemm et al. Z. Anorg. Allg. Chem. 1948, 256, 15.

H. Schnöckel et al. Inorg. Chem. 1989, 28, 2895.

The Al(I) with Cp* ligand

11

H. Schnöckel et al. Angew. Chem. Int. Ed. Engl. 1991, 30, 564.

H. W. Roesky et al. Angew. Chem. Int. Ed. Engl. 1993, 32, 1729.

The Al(I) with Cp* ligand

12

The Al(I) with Cp* ligandDerivatives

H. W. Roesky H. Schnöckel

H. Schnöckel H. W. Roesky R. A. Fischer

Angew. Chem. Int. Ed. 1998, 37, 1952. J. Organomet.Chem. 1998 , 561, 203.

J. Organomet.Chem. 1999 , 579, 373. Organometallics 2003, 22, 3637. Z. Anorg. Allg. Chem. 2005, 631, 2756.

H. Schnöckel

Organometallics 1998, 17, 1894.

[(t-Bu)3SiAl]4

[(Me3Si)3SiAl]4

Cp*3Al3AlN(SiMe3)2[(Me3Si)3CAl]4

[2,6-iPr2C6H3N(SiMe3)Al]4[Al(C5Me4Ph)]4

13

The Al(I) with Cp* ligandReactivity

R. Ahlrichs et al. Angew. Chem. Int. Ed. 1994, 33, 199.M. Kaupp et al. Inorg. Chem. 2016, 55 ,4915.

14A. H. Cowley et al. J. Chem. Soc., Dalton Trans. 1998, 1937

NH

H2C Al3+

Al3+

HN

CH2

Cp*

Cp*

AlN

AlN

Al

Al

Cp* N

Cp* N

Cp*Cp*

SiMe3

SiMe3

SiMe3

SiMe3

N

Al N

AlR

RCp*

Cp*

R = Si(i-Pr)3SiPh3Si(t-Bu)3

(Cp*Al)4-2 N2

4 Me3SiN3

(Cp*Al)4 toluene-4 N2

24 R3SiN3

(Cp*Al)4

2 MesN3

H. W. Roesky et al. Angew. Chem. Int. Ed. 1994, 33, 969.H. W. Roesky et al. Organometallics. 1996, 15, 5252.

toluene/60 °CN

AlN MesMes

Cp*

4N NMes Mes4(Cp*Al)4


15H. Schnöckel et al. Angew. Chem. Int. Ed. 1996, 35, 2875.H. Schnöckel et al. Z. Anorg. Allg. Chem. 2000, 626, 1557.

H. W. Roesky et al. Angew. Chem. Int. Ed. 1995, 34, 919.


16A. H. Cowley et al. Chem. Commun. 2001, 75.S. Schulz et al. Organometallics 2006, 25 ,5487.

The Al(I) with Cp* ligandFunction as Ligands

T. K. Woo et al. Organometallics 2003, 22, 1266.

17R. A. Fischer et al. Angew. Chem. Int. Ed. 2004, 43, 2299.

Ni(cod)2 [Ni(AlCp*)3] Ni

AlCp*

Et3Si

H

AlCp*

AlCp*

M

AlCp*

*CpAlAlCp*

AlCp*

Ni

AlCp*

*CpAlAlCp*

AlCp*

NMe2

Pd

Me2N Cl

Cl

-2 cod

HSiEt3

C6H6

n-hexane

C6H6- HSiEt3

partial decomposition

1/4 Cp*Aln-hexane - HSiEt3

hexane, 80 °C- TMEDA

- AlCp* Cl2

M = Ni; Pd

3 Cp*Al

1/4 Cp*Al

H1/4 Cp*Al

5 AlCp*


18

R. A. Fischer et al. Chem.-Eur. J. 2005, 11, 1636.R. A. Fischer et al. Dalton Trans., 2009, 322.R. A. Fischer et al. Inorg. Chem. 2017, 56, 3517.


19

Contents

20

The Al(I) with β-diketiminates

C. Cui, H. W. Roesky et al. Angew. Chem. Int. Ed. 2000, 39, 4274.C. Cui et al. Organometallics 2007, 26, 1039.

NH

NAr

Ar

AlMe3

-CH4 NAl

NAr

Ar

Me

Me

2 I2-2 MeI N

AlN

Ar

Ar

I

I

2 K, toluene-2 KI N

AlN

Ar

Ar

NH

Nt-Bu

t-Bu

Ar

Ar

AlEt3

-EtH NAl

Nt-Bu

t-Bu

Ar

Ar

Et

Et

2 I2-2 MeI N

AlN

t-Bu

t-Bu

Ar

Ar

I

I

2 K, toluene-2 KI N

AlN

t-Bu

t-Bu

Ar

Ar

Ar = 2,6-iPr2C6H3

21

H. W. Roesky et al. Angew. Chem. Int. Ed. 2004, 43, 3443.H. W. Roesky et al. Angew. Chem. Int. Ed. 2004, 43, 6190.H. W. Roesky et al. J. Am. Chem. Soc. 2005, 127, 10170.C. Cui et al. Organometallics 2007, 26, 1039.

The Al(I) with β-diketiminatesReactivity (with P4, S8, O2, and H2O)

22H. W. Roesky et al. Organometallics 2005, 24, 6420.

NAl

NAr

ArN N

NNR

RN

AlN

Ar

Ar

2 RN3, toluene

- N2 NAl

NAr

Ar

N

Trip

Trip

2,6-Trip2C6H3N3

toluene, -N2

NAl

NAr

Ar

NR

N N NR

Ar = 2,6-iPr2C6H3 Trip = 2,4,6-iPr3C6H2

R

2,6-Trip2C6H3

SiMe3

SiPh3

The Al(I) with β-diketiminatesReactivity (with azides)

H. W. Roesky et al. Angew. Chem. Int. Ed. 2000, 39, 4531.P. P. Power, H. W. Roesky et al. J. Am. Chem. Soc. 2001, 123, 9091.

NAl

NAr

ArN

AlN

Ar

Ar

N Sitoluene, -N2

t-BuSi(N3)3N3

N3

t-BuN

AlN

Ar

Ar

N3N Si

t-BuN3

NAl

NAr

Ar

N3

N

N3

N NAl

NAr

Ar

Si

Si

N3 t-Bu

t-Bu N3

Ar = 2,6-iPr2C6H3

[2+2]cycloaddition 1/2

23H. W. Roesky et al. Eur. J. Inorg. Chem. 2006, 128, 5100.

The Al(I) with β-diketiminatesReactivity (with other nitrogenous compounds)

P. P. Power et al. Angew. Chem. 2005, 117, 5220.H. W. Roesky et al. J. Am. Chem. Soc. 2006, 128 ,5100.

NAl

NAr

Ar

N

NNAl

NAr

Ar

Ph

Ph

Ph

Ph-N2

2 Ph2CN2, 80 °C

Ar = 2,6-iPr2C6H3oxidative addition

Ph2C=N-N=CPh2 2 Ph2CN2

H. W. Roesky et al. Eur. J. Inorg. Chem. 2004, 2004, 4046.

24M. R. Crimmin et al. Angew. Chem. Int. Ed. 2015, 51, 15994.G. I. Nikonov et al. Organometallics 2015, 34 ,5363.

G. I. Nikonov et al. J. Am. Chem. Soc. 2014, 136, 9195.G. I. Nikonov et al. Inorg.Chem. 2016, 55, 9099.

The Al(I) with β-diketiminatesReactivity (with molecules containing σ-bonds)

25

The Al(I) with β-diketiminatesReactivity (with unsaturated bonds)

G. I. Nikonov et al. Angew. Chem. Int. Ed. 2016, 55, 13306.

G. I. Nikonov et al. J. Am. Chem. Soc. 2017, 139, 8804.G. I. Nikonov et al. Inorg.Chem. 2016, 56 ,5993.

26

H. W. Roesky et al. Eur. J. Inorg. Chem. 2004, 2004, 4046.H. W. Roesky et al. Chem. Commun.2017, 53, 2543.H. W. Roesky et al. Angew. Chem. Int. Ed. 2005, 44, 7072.R. Kinjo et al. Chem.-Eur. J. 2016, 22 ,1922.

NAl

NAr

Ar

Ar=2,6-iPrC6H3

2PhB(OH)2

toluene NAl

NAr

Ar

HO

BPh

OH

HO

BO

HPh

-H2, -H2O

NAl

NAr

Ar

O

O B

BO

The Al(I) with β-diketiminatesReactivity (with other reagents)

H. W. Roesky et al. J. Am. Chem. Soc. 2006, 128, 12406.

27

Contents

28S. Aldridge et al. Nature 2018, 557, 92.

The Al(I) anionsDiamido Aluminyl Systems

29S. Aldridge et al. Nature. 2018, 557, 92.


30S. Aldridge et al. J. Am. Chem. Soc. 2019, 141, 11000.

O

tBu

tBu

N

N

Al

Dipp

Dipp

K

KO

tBu

tBu

N

N

Al

Dipp

Dipp 2,2,2 - cryptTetrahydrofuran

r.t., 30 min

Dipp

Dipp

Al

N

N

tBu

tBu

O

1 2

K(2,2,2-crypt)

N O

O

N

O

OO

O

2,2,2 - crypt

The Al(I) anionsC-C Bond Activation of Benzene

31

Dipp

Dipp

Al

N

N

tBu

tBu

O

2 Me2SnCl2 (2 equiv.)C6H6

r.t., 18 h

Dipp

Dipp

Al

N

N

tBu

tBu

OCl

ClSn Sn

Cl Cl

Me Me

MeMe

3 6 7

S. Aldridge et al. J. Am. Chem. Soc. 2019, 141, 11000

The Al(I) anionsC-C Bond Activation of Benzene

32S. Aldridge et al. Angew. Chem. Int. Ed. 2019, 58, 17265.

The Al(I) anionsAluminium Oxide Ion


The Al(I) anionsAluminium Oxide Ion


The Al(I) anionsMolecular Aluminium Imide

37S. Aldridge et al. Nat. Chem. 2019, 11, 237.

Dipp

Dipp

Al

N

N

tBu

tBu

OO

N

N

Dipp

Dipp

tBu

tBu

Al Al

tBu

tBu

Dipp

Dipp

N

N

O

K

K

Au

AuI

PPh3

PPh3

2 Ph3PAuI

- KI - KI

Dipp

Dipp

Al

N

N

tBu

tBu

O

tBu3PAuIAu PtBu3

19 20

The Al(I) anionsNucleophilic Gold Complex

38M. P. Coles et al. Angew. Chem. Int. Ed. 2019, 58, 1489.

The Al(I) anionsReaction with COT


The Al(I) anionsReaction with CO2


NSiO

Si NAl

N SiO

SiNAl

K

K

iPr

iPr

iPr

iPr

iPr

iPr

iPriPr

CS2 (2 equiv)

NSiO

Si NAl

N SiO

SiNAl

iPr

iPr

iPr

iPr

iPr

iPr

iPriPr

NSiO

Si NAl

iPr

iPr

iPriPr

S

SC S

K4

OEt2

CS2 (4 equiv)SS S

SC

C

K

K

29

30

The Al(I) anionsC-C Bond Formation


The Al(I) anionsC-C Bond Formation

43M. S. Hill et al. Angew. Chem. Int. Ed. 2020, 59, 3928.

The Al(I) anionsAlkaline Earth Compounds

44S. Harder et al. Angew. Chem. Int. Ed. 2020, 59, 15982.

S. Harder et al. Angew. Chem. Int. Ed. 2018, 57, 14169.S. Harder et al. Angew. Chem. Int. Ed. 2019, 58, 15496.


45S. Harder et al. Angew. Chem. Int. Ed. 2020, 59, 15982.

N AlNAr

Ar

RK

C6H6, 5 °C, 3 h

-RH, 2x NAl

NAr

Ar

NAl

NAr

ArK

K

KCH(SiMe3)2

34


46R. Kinjo et al. J. Am. Chem. Soc. 2020, 142, 9057.

The Al(I) anionsAlkyl Amino Aluminyl Systems

AlN

Me3Si SiMe3

Ad

[K(12C4)2]

BH3 SMe2 (3.0 eq.)

Et2O, r.t., 36 h75%

AlN

Me3Si SiMe3

Ad

HBB

H

H

H

HH

[K(12C4)2]

38 39

47

The Al(I) anionsAlkyl Amino Aluminyl Systems

R. Kinjo et al. J. Am. Chem. Soc. 2020, 142, 9057.

AlN

Me3Si SiMe3

Ad

[K(12C4)2]

SiH3Ph(1.1 eq.)

Et2O, r.t., 5 min66%

AlN

Me3Si SiMe3

Ad

SiH2Ph

H

[K(12C4)2]

AlN

Me3Si SiMe3

Ad

NH2

H

[K(12C4)2]NH3 (excess)

(2.5 eq.)

Et2O, r.t., 4 h33%

AlN

Me3Si SiMe3

Ad

[K(12C4)2]

Et2O, _50 C, 5 min44%

40

41

42

48

The Al(I) anionsAlkyl Aluminyl Systems

M. Yamashita et al. Nat. Chem. 2020, 12, 36.

Al

Me3Si SiMe3

SiMe3Me3Si

K(tol)2

r.t., 2.5 h79%

Al

Me3Si SiMe3

SiMe3Me3Si

K(tol)2H

MeOTf

Toluene_35 C

84%

Me3Si SiMe3

SiMe3Me3Si

Al Me

ClMe3Si SiMe3

SiMe3Me3Si

AlK(tol)2

Me3Si SiMe3

SiMe3Me3Si

Al Cl+

Me3Si SiMe3

SiMe3Me3Si

Al

FF

FF

F

F

(x equiv.)

Toluene _35 Cx = 0.5; 48, 70%x = 1; 47: 48 = 4 :3x = 10, 47:48 = 3 : 1

Me3SiMe3Si

SiMe3Me3Si

Al

F

K(tol)2

F FF

FF

Me3SiMe3Si

SiMe3Me3Si

Al

F

K(tol)2

+SiMe3SiMe3

Me3Si SiMe3

Al

F

(tol)2K

FF

F F

44

45

46

47 48

49

M. Yamashita and co-authors, Chem. Eur. J. 2020, 26, 4520.

Al

Me3Si SiMe3

SiMe3Me3Si

Al =

Al

anthracene(3.0 equiv.)

(5.0 equiv)Ph Ph

(3.0 equiv)

(1.0 equiv)

AlK(tol)2

Al K(tol)2

Ph

Ph(Z) or (E)

K(OEt2)2

1)

2) [2.2.2]-cryptandPh

Al

Ph

trans-5 (85%)

(sole product)

68%

Al

[K[2.2.2]-cryptand] +

M. Yamashita et al. Chem. Eur. J. 2020, 26, 2174.

The Al(I) anionsAlkyl Aluminyl Systems

50

H. Braunschweig et al. J. Am. Chem. Soc. 2019, 141, 16954.

P. P. Power et al. J. Am. Chem. Soc. 2020, doi.org/10.1021/jacs.0c10222.

Other Monomeric Al(I) species

[LiAlH3AriPr8]

3 CH3IEt2O, 0 oC

-LiI-3 CH4

AlI2AriPr8

Na/NaClhexane

iPr

iPr

iPr

iPr

iPr

iPr

iPr

iPr

Al

51

Summary

Synthesis reactivity(Cp*Al)4

Aluminyl Anion

Small molecule activation

Function as ligand

Reactions with organic reagents

Prospect

Catalysis

New ligand

Chiral ligandSmall moleculetransformation

Catalysis

New reaction

52

Thanks

59Makoto Yamashita and co-authors, Chem. Eur. J. 2020, 26, 2174.

60Makoto Yamashita and co-authors, Chem. Eur. J. 2020, 26, 2174.

gaining new vitality: chemistry of monovalent aluminum species

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