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The Chemistry of Frustrated Lewis Pairs

MacMillan Group Meeting


Tracy Liu
4 December 2013

RR
B
R

R
N

R
R

RR
B
R

R
N

R
R

RR
B
R

R
N

R
R

R
R

B
R

RR
B

R
N

RR

B
R

H2
R

R
B

R
R

B
R

RR
B

R
N

RR

B
R

H2
R

heat

R
R

B
R

Number of Publications

Rapid Emergence of FLP Chemistry

100
80
60
40
20
0

2000

2006

2009

2012

289 total publications in FLP chemistry


Leading Academics:
Douglas W. Stephan, University of Toronto, Canada
Gerhard Erker, Westflische Wilhelms-Universitt Mnster, Germany
Imre Ppai, Chemical Research Cent. of the Hungarian Acad. of Sciences, Hungary

The Advent of FLP Chemistry


1942 - Brown makes an
interesting observation

Me
N
Me

Me
BF 3

BF 3

BMe 3

No Reaction

Me

Brown, H. C.; Schlesinger, H. I. JACS, 1942, 64, 325-329.

The Advent of FLP Chemistry


1942 - Brown makes an
interesting observation

Me
N
Me

Me
BF 3

BF 3

BMe 3

No Reaction

Me

Brown, H. C.; Schlesinger, H. I. JACS, 1942, 64, 325-329.

The Advent of FLP Chemistry


1942 - Brown makes an
interesting observation

1959 - Wittig finds PPh 3 and BPh 3


does not form an adduct

Mg

PPh 3

Br

PPh 3
BPh 3

BPh 3

No formation of classical Lewis Acid/Base adduct

Wittig, G.; Benz, E. Chem. Ber., 1959, 92, 1999-2013.

The Advent of FLP Chemistry


1942 - Brown makes an
interesting observation

1966 - Tochtermann reports Ph 3Cand BPh 3 trap across olefins;


coining of the term "FLP"
1959 - Wittig finds PPh 3 and BPh 3
does not form an adduct

BPh 3

[Ph 3C-]Na+

Ph 3C

and

BPh 3

Ph 3C

BPh 3

no observation of polybutadiene

Tochtermann, W. ACIE, 1966, 5, 351-371.

The Advent of FLP Chemistry


2006 - Stephan finds FLPs
can reversibly split H 2

1942 - Brown makes an


interesting observation

1966 - Tochtermann reports Ph 3Cand BPh 3 trap across olefins;


coining of the term "FLP"
1959 - Wittig finds PPh 3 and BPh 3
does not form an adduct

Me

F
F

Me

PH

B(C 6F 5)3

(Me 3C6H 2)2P

B(C 6F 5)2

H
Me 2

Me 2SiHCl

F
H

(Me 3C6H 2)2P

B(C 6F 5)2

H
F

Welch, G. C.; San Juan, R. R.; Masuda, J. D.; Stephan, D. W. Science, 2006, 314, 1124-1126.

The Advent of FLP Chemistry


2006 - Stephan finds FLPs
can reversibly split H 2

1942 - Brown makes an


interesting observation

1966 - Tochtermann reports Ph 3Cand BPh 3 trap across olefins;


coining of the term "FLP"
1959 - Wittig finds PPh 3 and BPh 3
does not form an adduct

F
H

(Me 3C6H 2)2P

heat

B(C 6F 5)2

(Me 3C6H 2)2P

B(C 6F 5)2

H2

H
F

Welch, G. C.; San Juan, R. R.; Masuda, J. D.; Stephan, D. W. Science, 2006, 314, 1124-1126.

The Advent of FLP Chemistry


2006 - Stephan finds FLPs
can reversibly split H 2

1942 - Brown makes an


interesting observation

1966 - Tochtermann reports Ph 3Cand BPh 3 trap across olefins;


coining of the term "FLP"
1959 - Wittig finds PPh 3 and BPh 3
does not form an adduct

F
H

(Me 3C6H 2)2P

heat

B(C 6F 5)2

(Me 3C6H 2)2P

B(C 6F 5)2

H2

H
F

Welch, G. C.; San Juan, R. R.; Masuda, J. D.; Stephan, D. W. Science, 2006, 314, 1124-1126.

The Advent of FLP Chemistry


2006 - Stephan finds FLPs
can reversibly split H 2

1942 - Brown makes an


interesting observation

1966 - Tochtermann reports Ph 3Cand BPh 3 trap across olefins;


coining of the term "FLP"
1959 - Wittig finds PPh 3 and BPh 3
does not form an adduct

2007 - FLPs catalytically


perform hydrogenations

B(C 6F 5)2

(tBu) 2P
N

tBu

(5 mol %)
1 atm H 2

Ph

HN

tBu

Ph

98%
(C 6F 5)Ph2P (20 mol %)
B(C 6F 5)3 (20 mol %)
Ph

Ph

5 bar H 2

Me
Ph

Ph

99%
Chase, P.A.; Welch, G. C.; Jurca, T.; Stephan, D. W. ACIE, 2007, 46, 8050-8053.
Greb, L.; Ona-Burgos, P.; Schirmer, B.; Grimme, S.; Stephan, D. W.; Paradies, J. ACIE, 2012, 51, 10164-10168.

The Advent of FLP Chemistry


2006 - Stephan finds FLPs
can reversibly split H 2

1942 - Brown makes an


interesting observation

2008 - FLPs reversibly


bind CO2

1966 - Tochtermann reports Ph 3Cand BPh 3 trap across olefins;


coining of the term "FLP"
1959 - Wittig finds PPh 3 and BPh 3
does not form an adduct

tBu 3P

B(C 6F 5)3

2007 - FLPs catalytically


perform hydrogenations

CO2, 25 C

(tBu) 3P

B(C 6F 5)3
O

-CO2, 80 C
vacuum, 5 hrs

Mmming, C. M.; Otten, E.; Kehr, G.; Frlich, R.; Grimme, S.; Stephan, D. W.; Erker, G. ACIE, 2009, 48, 6643-6646.

The Advent of FLP Chemistry


2006 - Stephan finds FLPs
can reversibly split H 2

1942 - Brown makes an


interesting observation

2008 - FLPs reversibly


bind CO2

1966 - Tochtermann reports Ph 3Cand BPh 3 trap across olefins;


coining of the term "FLP"
1959 - Wittig finds PPh 3 and BPh 3
does not form an adduct

2007 - FLPs catalytically


perform hydrogenations

Me

Me
B(C 6F 5)2

OMe
Me
N

2010 - Asymmetric
hydrogenation
of imines with FLPs

Ph

OMe

HN

(5 mol %)
Me

tBu 3P (5 mol %)
25 bar H 2

Me

>99%
81% ee

Chen, D.; Wang, Y.; Klankermeyer, J. ACIE, 2010, 49, 9475-9578.

The Advent of FLP Chemistry


2006 - Stephan finds FLPs
can reversibly split H 2

1942 - Brown makes an


interesting observation

1966 - Tochtermann reports Ph 3Cand BPh 3 trap across olefins;


coining of the term "FLP"
1959 - Wittig finds PPh 3 and BPh 3
does not form an adduct

2008 - FLPs reversibly


bind CO2

2010 - Asymmetric
hydrogenation
of imines with FLPs

2007 - FLPs catalytically


perform hydrogenations

I. Theories on the Mechanism of H 2 Activation


II. Applications of FLPs in Hydrogenation Reactions
and Storage of Small Molecules

The Advent of FLP Chemistry


2006 - Stephan finds FLPs
can reversibly split H 2

1942 - Brown makes an


interesting observation

1966 - Tochtermann reports Ph 3Cand BPh 3 trap across olefins;


coining of the term "FLP"
1959 - Wittig finds PPh 3 and BPh 3
does not form an adduct

2008 - FLPs reversibly


bind CO2

2010 - Asymmetric
hydrogenation
of imines with FLPs

2007 - FLPs catalytically


perform hydrogenations

I. Theories on the Mechanism of H 2 Activation


II. Applications of FLPs in Hydrogenation Reactions
and Storage of Small Molecules

Two Competing Models on the Mechanism of H 2 Activation

H
A

R
R

D * donation

H
H

D
R

R
R

A donation

Electron Transfer Model

R 3P

BR 3

Electric Field Model

Initial Hypotheses on the Mechanism of H 2 Activation

tBu 3P

B(C 6F 5)3

Mes 3P

B(C 6F 5)3

H2
1 atm
H2
1 atm

[tBu 3PH][HB(C 6F 5)3]

[Mes 3PH][HB(C 6F 5)3]

Welch, C.; Stephan, D. W. JACS, 2007, 129 , 1880-1881.

Initial Hypotheses on the Mechanism of H 2 Activation

tBu 3P

B(C 6F 5)3

Mes 3P

B(C 6F 5)3

H2

[tBu 3PH][HB(C 6F 5)3]

1 atm
H2

[Mes 3PH][HB(C 6F 5)3]

1 atm

R 3P
H
BR 3
H
(H 2) p (B)

PR 3 + BR 3

R 3P

[R 3PH][HBR 3]

H
BR 3

LP (P) * (H 2)

Welch, C.; Stephan, D. W. JACS, 2007, 129 , 1880-1881.

First DFT Study on the Mechanism of H 2 Activation

tBu 3P ------ B(C 6F 5)3

Multiple H-bonds between CH---F groups give rise to a preorganized complex


Non-directional dispersion forces between tBu and C6F 5 groups render the complex flexible

Rokob, T. A.; Hamza, A.; Stirling, A.; Sos, T.; Ppai, I. ACIE, 2008, 120 , 2469-2472.

First DFT Study on the Mechanism of H 2 Activation

tBu 3P --- HH --- B(C 6F 5)3

Located T.S. features a nearly linear PHHB axis


H 2 bond elongated from 0.74 A to 0.79 A indicative of an early T.S.
10.4 kcal/mol higher than tBu 3P---B(C 6F 5)3 + H 2

Rokob, T. A.; Hamza, A.; Stirling, A.; Sos, T.; Ppai, I. ACIE, 2008, 120 , 2469-2472.

First DFT Study on the Mechanism of H 2 Activation

tBu 3P --- HH --- B(C 6F 5)3

Discovered significant H 2 polarization


Electron transfer proceeds via simultaneous tBu 3P (H 2) and (H 2) B(C 6F 5)3 donation

Rokob, T. A.; Hamza, A.; Stirling, A.; Sos, T.; Ppai, I. ACIE, 2008, 120 , 2469-2472.

First DFT Study on the Mechanism of H 2 Activation


The Electron Transfer Model

Non-bonding interactions between bulky substituents lead to a higher E frustrated complex

Rokob, T. A.; Hamza, A.; Stirling, A.; Sos, T.; Ppai, I. ACIE, 2008, 120 , 2469-2472.

First DFT Study on the Mechanism of H 2 Activation


The Electron Transfer Model

Non-bonding interactions between bulky substituents lead to a higher E frustrated complex


Frustration energy, Et, decreases the activation energy and renders hydrogen splitting
facile and highly exothermic via reactant state destabilization

Rokob, T. A.; Hamza, A.; Stirling, A.; Sos, T.; Ppai, I. ACIE, 2008, 120 , 2469-2472.

First DFT Study on the Mechanism of H 2 Activation


The Electron Transfer Model

Non-bonding interactions between bulky substituents lead to a higher E frustrated complex


Frustration energy, Et, decreases the activation energy and renders hydrogen splitting
facile and highly exothermic via reactant state destabilization
Non-bonding interactions between bulky substituents stabilizes both the T.S. and product
Rokob, T. A.; Hamza, A.; Stirling, A.; Sos, T.; Ppai, I. ACIE, 2008, 120 , 2469-2472.

An Alternative Mechanism of H 2 Activation

Mes

C6F 5

C6F 5
B
C6F 5

Mes

H2

Mes

C6F 5
H

Mes

Ph

Ph
Mes
Mes

Mes

H2

B
Ph

Mes

B
H

Ph
H

Linear T.S. not possible for certain tethered FLPs

Grimme, S.; Kruse, H.; Goerigk, L.; Erker, G. ACIE, 2010, 49, 1402-1405.

An Alternative Mechanism of H 2 Activation


Calculated T.S. employing a dispersion corrected DFT model:

(C 6F 5)3B ---- PtBu 3 + H 2

(C 6F 5)2B

PMes 2

H2

Calculated T.S. do not have a linear relationship along PHHB axis

Grimme, S.; Kruse, H.; Goerigk, L.; Erker, G. ACIE, 2010, 49, 1402-1405.

An Alternative Mechanism of H 2 Activation

incr. E

2 kcal/mol between
each line

2-D potential E surface for tBu 3P + B(C 6F 5)3 system

Grimme, S.; Kruse, H.; Goerigk, L.; Erker, G. ACIE, 2010, 49, 1402-1405.

An Alternative Mechanism of H 2 Activation

incr. E
peak

2 kcal/mol between
each line

Grimme, S.; Kruse, H.; Goerigk, L.; Erker, G. ACIE, 2010, 49, 1402-1405.

An Alternative Mechanism of H 2 Activation


artificial T.S.

peak

Ppai's non-dispersion corrected DFT model overestimated the PB bond distance


resulting in a T.S. that is otherwise not present

Grimme, S.; Kruse, H.; Goerigk, L.; Erker, G. ACIE, 2010, 49, 1402-1405.

An Alternative Mechanism of H 2 Activation


The Electric Field Model

R 3P

BR 3

Neglect the FLP as a molecular species


and replace it by an electric field
Polarization from electric field generated in
the interior of the FLP cavity allows for H 2 splitting

Grimme, S.; Kruse, H.; Goerigk, L.; Erker, G. ACIE, 2010, 49, 1402-1405.

An Alternative Mechanism of H 2 Activation


The Electric Field Model

R 3P

BR 3

Neglect the FLP as a molecular species


and replace it by an electric field
Polarization from electric field generated in
the interior of the FLP cavity allows for H 2 splitting

F = Electric field strength (a.u.)


(1 a.u. = 5.1422 x 1011 Vm-1)

Critical field strength needed for H 2 splitting is 0.05 0.06 a.u.


Grimme, S.; Kruse, H.; Goerigk, L.; Erker, G. ACIE, 2010, 49, 1402-1405.

An Alternative Mechanism of H 2 Activation


The Electric Field Model

F = Electric field strength (a.u.)


(1 a.u. = 5.1422 x 1011 Vm-1)

Critical field strength needed for H 2 splitting is 0.05 0.06 a.u.

tBu

C6F 5

P
B
tBu C6F 5
C6F 5
tBu

0.04 - 0.06 a.u.

C6F 5
Mes
P

B
C6F 5

Mes

0.04 - 0.06 a.u.


Grimme, S.; Kruse, H.; Goerigk, L.; Erker, G. ACIE, 2010, 49, 1402-1405.

An Alternative Mechanism of H 2 Activation


The Electric Field Model

H-bonding interactions form the FLP while non-directional dispersion forces instill
flexibility allowing H 2 entry termed the "preparation step"

Grimme, S.; Kruse, H.; Goerigk, L.; Erker, G. ACIE, 2010, 49, 1402-1405.

An Alternative Mechanism of H 2 Activation


The Electric Field Model

H-bonding interactions form the FLP while non-directional dispersion forces instill
flexibility allowing H 2 entry termed the "preparation step"
Activation energy is the "preparation step"; after entrance H 2 splitting is barrierless

Grimme, S.; Kruse, H.; Goerigk, L.; Erker, G. ACIE, 2010, 49, 1402-1405.

An Alternative Mechanism of H 2 Activation


The Electric Field Model

H-bonding interactions form the FLP while non-directional dispersion forces instill
flexibility allowing H 2 entry termed the "preparation step"
Activation energy is the "preparation step"; after entrance H 2 splitting is barrierless
No molecular orbitals arguments invoked; believe this accounts for the similar reactivity
of chemically different FLPs

Grimme, S.; Kruse, H.; Goerigk, L.; Erker, G. ACIE, 2010, 49, 1402-1405.

The Electron Transfer Model Revisited

C6F 5

tBu
P
tBu
tBu

tBu

B
C6F 5

C
C6F 5

C6F 5

N
N
tBu

C6F 4H

B
C6F 5

C6F 5

Mes

B
C6F 4H

Rokob, T. A.; Bak, I.; Stirling, A.; Hamza, A.; Ppai, I. JACS, 2013, 135 , 4425-4437.

The Electron Transfer Model Revisited

C6F 5

tBu
P
tBu
tBu

tBu

B
C6F 5

C
C6F 5

C6F 5

N
N
tBu

C6F 4H

B
C6F 5

C6F 5

Mes

B
C6F 4H

Rokob, T. A.; Bak, I.; Stirling, A.; Hamza, A.; Ppai, I. JACS, 2013, 135 , 4425-4437.

The Electron Transfer Model Revisited

F = Electric field strength (a.u.)


(1 a.u. = 5.1422 x 1011 Vm-1)

At the "critical field" of 0.06 a.u., the activation energy is 75 kcal/mol

Grimme, S.; Kruse, H.; Goerigk, L.; Erker, G. ACIE, 2010, 49, 1402-1405.
Rokob, T. A.; Bak, I.; Stirling, A.; Hamza, A.; Ppai, I. JACS, 2013, 135 , 4425-4437.

The Electron Transfer Model Revisited

F = Electric field strength (a.u.)


(1 a.u. = 5.1422 x 1011 Vm-1)

At the "critical field" of 0.06 a.u., the activation energy is 75 kcal/mol


Only at higher electric fields, 0.09 a.u. and above, does the activation energy lower
to a reasonable range (20 kcal/mol or lower)

Grimme, S.; Kruse, H.; Goerigk, L.; Erker, G. ACIE, 2010, 49, 1402-1405.
Rokob, T. A.; Bak, I.; Stirling, A.; Hamza, A.; Ppai, I. JACS, 2013, 135 , 4425-4437.

The Electron Transfer Model Revisited

F = Electric field strength (a.u.)


(1 a.u. = 5.1422 x 1011 Vm-1)

At the "critical field" of 0.06 a.u., the activation energy is 75 kcal/mol


Only at higher electric fields, 0.09 a.u. and above, does the activation energy lower
to a reasonable range (20 kcal/mol or lower)
Only at field strengths above 0.1 a.u., does H 2 splitting become "barrierless"
Grimme, S.; Kruse, H.; Goerigk, L.; Erker, G. ACIE, 2010, 49, 1402-1405.
Rokob, T. A.; Bak, I.; Stirling, A.; Hamza, A.; Ppai, I. JACS, 2013, 135 , 4425-4437.

The Electron Transfer Model Revisited

C6F 5

tBu
P
tBu
tBu

tBu

B
C6F 5

C
C6F 5

C6F 5

N
N
tBu

C6F 4H

B
C6F 5

C6F 5

Mes

B
C6F 4H

Rokob, T. A.; Bak, I.; Stirling, A.; Hamza, A.; Ppai, I. JACS, 2013, 135 , 4425-4437.

The Electron Transfer Model Revisited

C6F 5

tBu
P
tBu
tBu

tBu

B
C6F 5

C
C6F 5

C6F 5

N
N
tBu

C6F 4H

B
C6F 5

C6F 5

Mes

B
C6F 4H

Rokob, T. A.; Bak, I.; Stirling, A.; Hamza, A.; Ppai, I. JACS, 2013, 135 , 4425-4437.

The Electron Transfer Model Revisited

C6F 5

tBu
P
tBu
tBu

tBu

B
C6F 5

C
C6F 5

C6F 5

N
N
tBu

C6F 4H

B
C6F 5

C6F 5

Mes

B
C6F 4H

EFs within FLP cavities are not homogeneous and are not always strong enough to effect H 2 splitting

Rokob, T. A.; Bak, I.; Stirling, A.; Hamza, A.; Ppai, I. JACS, 2013, 135 , 4425-4437.

The Electron Transfer Model Revisited

Me
tBu
P
tBu
tBu

tBu

C
N

tBu
Mes
N

+ B(C 6F 5)3

+ B(C 6F 5)3

+ B(C 6F 5)3

Mes

C6F 5
tBu

C6F 5
Me

C6F 5

C6F 5
P

Me

Me

tBu

Ph
P

Ph

Rokob, T. A.; Bak, I.; Stirling, A.; Hamza, A.; Ppai, I. JACS, 2013, 135 , 4425-4437.

The Electron Transfer Model Revisited


0.09 a.u.

For none of the FLPs studied is the EF along the H 2 axis high enough to permit H 2 splitting
Me
tBu
P
tBu
tBu

tBu

C
N

tBu
Mes
N

+ B(C 6F 5)3

+ B(C 6F 5)3

+ B(C 6F 5)3

Mes

C6F 5
tBu

C6F 5
Me

C6F 5

C6F 5
P

Me

Me

tBu

Ph
P

Ph

Rokob, T. A.; Bak, I.; Stirling, A.; Hamza, A.; Ppai, I. JACS, 2013, 135 , 4425-4437.

The Electron Transfer Model Revisited

H
A

D * donation
H

H
R
R

H
H

D
R

R
R
R

A donation

Use of dispersion corrected DFT basis set results in a generally bent DHHA geometry
explained by frontier orbitals aligning themselves for optimal orbital overlap
Deviation from ideal 180 D---H 2 angle and 90 H 2---A angle due to polarization of the
/ * orbitals of H 2

Rokob, T. A.; Bak, I.; Stirling, A.; Hamza, A.; Ppai, I. JACS, 2013, 135 , 4425-4437.

The Advent of FLP Chemistry


2006 - Stephan finds FLPs
can reversibly split H 2

1942 - Brown makes an


interesting observation

1966 - Tochtermann reports Ph 3Cand BPh 3 trap across olefins;


coining of the term "FLP"
1959 - Wittig finds PPh 3 and BPh 3
does not form an adduct

2008 - FLPs reversibly


bind CO2

2010 - Asymmetric
hydrogenation
of imines with FLPs

2007 - FLPs catalytically


perform hydrogenations

I. Theories on the Mechanism of H 2 Activation


II. Applications of FLPs in Hydrogenation Reactions
and Storage of Small Molecules

The First Example of Catalytic Hydrogenations with FLPs


Hydrogenation of Imines, Nitriles, and Aziridines

F
PR 2

(C 6F 5)2B
F

1 R = Mes
2 R = tBu

N
Ph

tBu

5 mol % cat.
1 atm H 2
80 C

HN

tBu

Ph

79% (1)
98% (2)

Chase, P. A.; Welch, C.; Jurca, T.; Stephan, D. W. ACIE, 2007, 46, 8050-8053.

The First Example of Catalytic Hydrogenations with FLPs


Hydrogenation of Imines, Nitriles, and Aziridines

F
PR 2

(C 6F 5)2B
F

1 R = Mes
2 R = tBu

tBu

5 mol % cat.
1 atm H 2
80 C

Ph

HN

tBu

Ph

79% (1)
98% (2)

Ph
N

Ph

SO2Ph

Ph

97% (1)
87% (2)

Ph

Ph

N
Ph

88% (1)

Ph

98% (1)

Chase, P. A.; Welch, C.; Jurca, T.; Stephan, D. W. ACIE, 2007, 46, 8050-8053.

The First Example of Catalytic Hydrogenations with FLPs


Hydrogenation of Imines, Nitriles, and Aziridines
Catalytic hydrogenation only possible for sterically hindered imines
F

Mes 2P

B(C 6F 5)2
F

N
Ph

Ph

F
HN

5 mol %
5 atm H 2
120 C

Ph

Ph

5%

Chase, P. A.; Welch, C.; Jurca, T.; Stephan, D. W. ACIE, 2007, 46, 8050-8053.

The First Example of Catalytic Hydrogenations with FLPs


Hydrogenation of Imines, Nitriles, and Aziridines
Catalytic hydrogenation only possible for sterically hindered imines
F

Mes 2P

B(C 6F 5)2
F

N
Ph

Ph

F
HN

5 mol %
5 atm H 2
120 C

Ph

Ph

5%

F Bn

H
N

Mes 2P

Bn

B(C 6F 5)2
F

adduct formation between Lewis Basic product


and FLP shuts down catalytic activity

Chase, P. A.; Welch, C.; Jurca, T.; Stephan, D. W. ACIE, 2007, 46, 8050-8053.

The First Example of Catalytic Hydrogenations with FLPs


Hydrogenation of Imines, Nitriles, and Aziridines
Catalytic hydrogenation only possible for sterically hindered imines
F

Mes 2P

B(C 6F 5)2
F

Ph

F
HN

5 mol %
5 atm H 2
120 C

Ph

Ph

Ph

5%

Protecting Imine with B(C 6F 5)3 recovers catalytic activity


F

Mes 2P

(C 6F 5)3B
Ph

B(C 6F 5)2
F

Ph

5 mol %
5 atm H 2
120 C

(C 6F 5)3B

Ph

Ph

57%

Chase, P. A.; Welch, C.; Jurca, T.; Stephan, D. W. ACIE, 2007, 46, 8050-8053.

The First Example of Catalytic Hydrogenations with FLPs


Hydrogenation of Imines, Nitriles, and Aziridines

Catalytic hydrogenation only possible for B(C 6F 5)3 protected nitriles

Mes 2P

B(C 6F 5)2

B(C 6F 5)3

5 mol %

5 atm H 2
120 C

F
HN

B(C 6F 5)3

R = Me, 75%
R = Ph, 84%

Only the amine is isolated (cannot isolate imine)

Chase, P. A.; Welch, C.; Jurca, T.; Stephan, D. W. ACIE, 2007, 46, 8050-8053.

The First Example of Catalytic Hydrogenations with FLPs


Hydrogenation of Imines, Nitriles, and Aziridines
F

Mes 2P

B(C 6F 5)2
F

H2

F
H

Mes 2P

B(C 6F 5)2

H
F

Chase, P. A.; Welch, C.; Jurca, T.; Stephan, D. W. ACIE, 2007, 46, 8050-8053.

The First Example of Catalytic Hydrogenations with FLPs


Hydrogenation of Imines, Nitriles, and Aziridines
F

Mes 2P

B(C 6F 5)2
F

F
H

H2

H
Mes 2P

H
Mes 2P

B(C 6F 5)2

B(C 6F 5)2

Ph
F

proton transfer

Ph

Chase, P. A.; Welch, C.; Jurca, T.; Stephan, D. W. ACIE, 2007, 46, 8050-8053.

The First Example of Catalytic Hydrogenations with FLPs


Hydrogenation of Imines, Nitriles, and Aziridines
F

HN

Mes 2P

F
N

B(C 6F 5)2
F

Ph

H2

H
Mes 2P

H
Mes 2P

B(C 6F 5)2

B(C 6F 5)2

Ph
F

proton transfer

Ph

Chase, P. A.; Welch, C.; Jurca, T.; Stephan, D. W. ACIE, 2007, 46, 8050-8053.

The First Example of Catalytic Hydrogenations with FLPs


Hydrogenation of Imines, Nitriles, and Aziridines
F

HN

Mes 2P

F
N

B(C 6F 5)2
F

Ph

H2

H
Mes 2P

H
Mes 2P

B(C 6F 5)2

B(C 6F 5)2

Ph
F

proton transfer

Ph

Proton transfer precedes hydride delivery


Increased rates with electron rich imines (R = tBu, 1 hr vs. R = SO2Ph, >10 hrs)
Chase, P. A.; Welch, C.; Jurca, T.; Stephan, D. W. ACIE, 2007, 46, 8050-8053.

The First Example of Catalytic Hydrogenations with FLPs


Hydrogenation of Imines, Nitriles, and Aziridines
F

Mes 2P

B(C 6F 5)2
F

H2

F
H

Mes 2P

B(C 6F 5)2

H
F

Chase, P. A.; Welch, C.; Jurca, T.; Stephan, D. W. ACIE, 2007, 46, 8050-8053.

The First Example of Catalytic Hydrogenations with FLPs


Hydrogenation of Imines, Nitriles, and Aziridines
F

Mes 2P

B(C 6F 5)2
F

F
(C 6F 5)3B
Ph

H2

H
Mes 2P

Mes 2P

B(C 6F 5)2

B(C 6F 5)2

H
F

hydride delivery
(C 6F 5)3B

Ph

Chase, P. A.; Welch, C.; Jurca, T.; Stephan, D. W. ACIE, 2007, 46, 8050-8053.

The First Example of Catalytic Hydrogenations with FLPs


Hydrogenation of Imines, Nitriles, and Aziridines
F
(C 6F 5)3B

H
N

Mes 2P

Ph

B(C 6F 5)2
F

Ph

(C 6F 5)3B

H2

H
Mes 2P

Mes 2P

B(C 6F 5)2

B(C 6F 5)2

H
F

hydride delivery
(C 6F 5)3B

Ph

Chase, P. A.; Welch, C.; Jurca, T.; Stephan, D. W. ACIE, 2007, 46, 8050-8053.

The First Example of Catalytic Hydrogenations with FLPs


Hydrogenation of Imines, Nitriles, and Aziridines
F
(C 6F 5)3B

H
N

Mes 2P

Ph

B(C 6F 5)2
F

Ph

(C 6F 5)3B

H2

H
Mes 2P

Mes 2P

B(C 6F 5)2

B(C 6F 5)2

H
F

hydride delivery
(C 6F 5)3B

Ph

Hydride delivery precedes proton transfer

Chase, P. A.; Welch, C.; Jurca, T.; Stephan, D. W. ACIE, 2007, 46, 8050-8053.

An Improved FLP
Hydrogenation of Ketimines and Enamines

H2
Mes 2P

B(C 6F 5)2

B(C 6F 5)3

Mes 2P
H

N
Ph

tBu

Mes 2P

B(C 6F 5)2

HN

20 mol %
2.5 bar H 2
r.t.

tBu

Ph

87%

Spies, P.; Schwendemann, S.; Lange, S.; Kehr, G.; Frhlich, R.; Erker, G. ACIE, 2008, 47, 7543-7546.

An Improved FLP
Hydrogenation of Ketimines and Enamines

H2
Mes 2P

B(C 6F 5)2

B(C 6F 5)3

Mes 2P
H

Mes 2P

tBu

B(C 6F 5)2

HN

20 mol %
2.5 bar H 2
r.t.

Ph

tBu

Ph

87%
O

N
N
Ph

tBu

70%
(5 mol %)

70%
(3 mol %)

Me

70%
(5 mol %)

70%
(10 mol %)

Spies, P.; Schwendemann, S.; Lange, S.; Kehr, G.; Frhlich, R.; Erker, G. ACIE, 2008, 47, 7543-7546.

Catalytic Hydrogenations Using only B(C6F 5 )3


Hydrogenation of Imines

N
Ph

tBu

B(C 6F 5)3 (cat.)


4 atm H 2
toluene, 25 C

(C 6F 5)3B
Ph

tBu

H 2N

4 atm H 2
toluene, 80 C

tBu
HB(C 6F 5)3

Ph

Chase, P. A.; Jurca, T.; Stephan, D. W. Chem. Comm., 2008, 1701-1703.

Catalytic Hydrogenations Using only B(C6F 5 )3


Hydrogenation of Imines

N
Ph

tBu

B(C 6F 5)3 (cat.)


4 atm H 2
toluene, 25 C

(C 6F 5)3B
Ph

tBu

H 2N

4 atm H 2
toluene, 80 C

tBu
HB(C 6F 5)3

Ph

Isolation of zwitterion suggests adduct formation with the product is reversible


and that the B(C 6F 5)3 catalyst can be recycled

Chase, P. A.; Jurca, T.; Stephan, D. W. Chem. Comm., 2008, 1701-1703.

Catalytic Hydrogenations Using only B(C6F 5 )3


Hydrogenation of Imines

N
Ph

tBu

B(C 6F 5)3 (cat.)


4 atm H 2
toluene, 25 C

(C 6F 5)3B

tBu

H 2N

4 atm H 2
toluene, 80 C

Ph

tBu
HB(C 6F 5)3

Ph

Isolation of zwitterion suggests adduct formation with the product is reversible


and that the B(C 6F 5)3 catalyst can be recycled

N
Ph

tBu

5 mol % B(C 6F 5)3


5 atm H 2
120 C

HN

tBu

Ph

89%

Chase, P. A.; Jurca, T.; Stephan, D. W. Chem. Comm., 2008, 1701-1703.

Catalytic Hydrogenations Using only B(C6F 5 )3


Hydrogenation of Imines

N
Ph

tBu

B(C 6F 5)3 (cat.)


4 atm H 2
toluene, 25 C

(C 6F 5)3B

tBu

H 2N

4 atm H 2
toluene, 80 C

Ph

tBu
HB(C 6F 5)3

Ph

Isolation of zwitterion suggests adduct formation with the product is reversible


and that the B(C 6F 5)3 catalyst can be recycled

B(C 6F 5)3

H2 +

N
R'

H
HB(C 6F 5)3
R'

Chase, P. A.; Jurca, T.; Stephan, D. W. Chem. Comm., 2008, 1701-1703.

Catalytic Hydrogenations Using only B(C6F 5 )3


Hydrogenation of Imines

N
Ph

tBu

B(C 6F 5)3 (cat.)

(C 6F 5)3B

4 atm H 2
toluene, 25 C

tBu

H 2N

4 atm H 2
toluene, 80 C

Ph

tBu
HB(C 6F 5)3

Ph

Isolation of zwitterion suggests adduct formation with the product is reversible


and that the B(C 6F 5)3 catalyst can be recycled

B(C 6F 5)3

H2 +

N
R'

H
R N B(C 6F 5)3
H

R'

H
HB(C 6F 5)3
R'

Chase, P. A.; Jurca, T.; Stephan, D. W. Chem. Comm., 2008, 1701-1703.

Catalytic Hydrogenations Using only B(C6F 5 )3


Hydrogenation of Imines

N
Ph

tBu

B(C 6F 5)3 (cat.)

(C 6F 5)3B

4 atm H 2
toluene, 25 C

tBu

H 2N

4 atm H 2
toluene, 80 C

Ph

tBu
HB(C 6F 5)3

Ph

Isolation of zwitterion suggests adduct formation with the product is reversible


and that the B(C 6F 5)3 catalyst can be recycled

NH

B(C 6F 5)3

H2 +

R'

N
R'

H
R N B(C 6F 5)3
H

R'

H
HB(C 6F 5)3
R'

Chase, P. A.; Jurca, T.; Stephan, D. W. Chem. Comm., 2008, 1701-1703.

Expanding the Scope to Oxygenated Substrates


Hydrogenation of Silyl Enol Ethers

PPh 2 PPh 2

H 2, r.t.

PPh 2 PPh 2
HB(C 6F 5)3

H 2, 60 C

Wang, H.; Frhlich, R.; Kehr, G.; Erker, G. Chem. Comm., 2008, 5966-5968.

Expanding the Scope to Oxygenated Substrates


Hydrogenation of Silyl Enol Ethers

PPh 2 PPh 2

H 2, r.t.

PPh 2 PPh 2
HB(C 6F 5)3

H 2, 60 C

OTMS
R

OTMS

20 mol % cat.
2 bar H 2, r.t.

R'

Wang, H.; Frhlich, R.; Kehr, G.; Erker, G. Chem. Comm., 2008, 5966-5968.

Expanding the Scope to Oxygenated Substrates


Hydrogenation of Silyl Enol Ethers

B(C 6F 5)3
H 2, r.t.

PPh 2 PPh 2

PPh 2 PPh 2
HB(C 6F 5)3

H2, 60 C

OTMS
R

2 bar H 2, r.t.

OTMS
OTMS

OTMS

OTMS

20 mol % cat.
R

OTMS

93%

OTMS
Me

tBu

Ph

R'

89%

86%

85%

>99%

Wang, H.; Frhlich, R.; Kehr, G.; Erker, G. Chem. Comm., 2008, 5966-5968.

Studies of Hantzsch Ester with B(C6F 5 )3 Unveils New Substrates


Hydrogenation of N-heterocycles

EtO

O
OEt

Me

N
H

Me

B(C 6F 5)3
-40 C

EtO

OEt
Me

N
H

Me

60%

EtO

HB(C 6F 5)3

-20 C

OEt

H
Me

B(C 6F 5)3

N
H

Me

55%
(70% at r.t.)

Webb, J. D.; Laberge, V. S.; Geier, S. J.; Stephan, D. W.; Crudden, C. M. Chem. Eur. J., 2010, 16 , 4895-4902.
Geier, S. J.; Chase, P. A.; Stephan, D. W. Chem. Comm., 2010, 46, 4884-4886.

Studies of Hantzsch Ester with B(C6F 5 )3 Unveils New Substrates


Hydrogenation of N-heterocycles

EtO

O
OEt

Me

N
H

Me

B(C 6F 5)3
-40 C

EtO

OEt
Me

N
H

Me

EtO

HB(C 6F 5)3

-20 C

60%

OEt

H
Me

B(C 6F 5)3

N
H

Me

55%
(70% at r.t.)

Observation of hydride delivery into pyridinium inspired


experimentation with N-heterocycle substrates

Webb, J. D.; Laberge, V. S.; Geier, S. J.; Stephan, D. W.; Crudden, C. M. Chem. Eur. J., 2010, 16 , 4895-4902.
Geier, S. J.; Chase, P. A.; Stephan, D. W. Chem. Comm., 2010, 46, 4884-4886.

Studies of Hantzsch Ester with B(C6F 5 )3 Unveils New Substrates


Hydrogenation of N-heterocycles

EtO

O
OEt

Me

N
H

Me

B(C 6F 5)3
-40 C

EtO

OEt
Me

N
H

EtO

HB(C 6F 5)3

-20 C

Me

60%

OEt

H
Me

B(C 6F 5)3

N
H

Me

55%
(70% at r.t.)

Observation of hydride delivery into pyridinium inspired


experimentation with N-heterocycle substrates

5 mol % B(C 6F 5)3


N

4 atm H 2, 2 hrs, r.t.


80%

N
H

HB(C 6F 5)3
N
H

Webb, J. D.; Laberge, V. S.; Geier, S. J.; Stephan, D. W.; Crudden, C. M. Chem. Eur. J., 2010, 16 , 4895-4902.
Geier, S. J.; Chase, P. A.; Stephan, D. W. Chem. Comm., 2010, 46, 4884-4886.

Studies of Hantzsch Ester with B(C6F 5 )3 Unveils New Substrates


Hydrogenation of N-heterocycles

EtO

OEt
Me

N
H

B(C 6F 5)3
-40 C

Me

EtO

OEt
Me

N
H

EtO

HB(C 6F 5)3

-20 C

Me

OEt

H
Me

60%

B(C 6F 5)3

N
H

Me

55%

Observation of hydride delivery into pyridinium inspired


experimentation with N-heterocycle substrates

5 mol % B(C 6F 5)3


2 hrs, r.t.

N
H

80%

N
H

80%

Ph

N
H

74%

Me
Me

N
H

88%

N
H

84%

Webb, J. D.; Laberge, V. S.; Geier, S. J.; Stephan, D. W.; Crudden, C. M. Chem. Eur. J., 2010, 16 , 4895-4902.
Geier, S. J.; Chase, P. A.; Stephan, D. W. Chem. Comm., 2010, 46, 4884-4886.

Aromatic Hydrogenation
Hydrogenation of Anilines to Cyclohexylamines
tBu
tBu

NH
Ph

B(C 6F 5)3
H 2, 25 C

tBu

NH 2
Ph

HB(C 6F 5)3

H2

NH 2
HB(C 6F 5)3

110 C
93%

Mahdi, T.; Heiden, Z. M.; Grimme, S.; Stephan, D. W. JACS, 2012, 134 , 4088-4091.

Aromatic Hydrogenation
Hydrogenation of Anilines to Cyclohexylamines
tBu
tBu

NH
Ph

B(C 6F 5)3

tBu

H 2, 25 C

NH 2

NH 2

H2

HB(C 6F 5)3

HB(C 6F 5)3

110 C

Ph

93%

iPr
NH 2

iPr

NH 2

iPr

NH 2

NH 2

Me

OMe

Me

Me

HB(C 6F 5)3

HB(C 6F 5)3

HB(C 6F 5)3

HB(C 6F 5)3

65%, 96 hrs

77%, 36 hrs

61%, 36 hrs

48%, 72 hrs

Mahdi, T.; Heiden, Z. M.; Grimme, S.; Stephan, D. W. JACS, 2012, 134 , 4088-4091.

Aromatic Hydrogenation
Hydrogenation of Anilines to Cyclohexylamines
tBu
tBu

NH
Ph

B(C 6F 5)3

tBu

H 2, 25 C

NH 2

NH 2

H2

HB(C 6F 5)3

HB(C 6F 5)3

110 C

Ph

93%

iPr
iPr

NH 2

NH 2

iPr

NH 2

NH 2

Me
Me

OMe

Me

HB(C 6F 5)3

HB(C 6F 5)3

HB(C 6F 5)3

HB(C 6F 5)3

65%, 96 hrs

77%, 36 hrs

61%, 36 hrs

48%, 72 hrs

Ph

5 mol % B(C 6F 5)3

N
Ph

Ph

H 2, 110 C

H 2N
Ph

HB(C 6F 5)3
Ph

50%, 96 hrs
Mahdi, T.; Heiden, Z. M.; Grimme, S.; Stephan, D. W. JACS, 2012, 134 , 4088-4091.

Hydrogenation of Non-Polar Substrates


Hydrogenation of Olefins

(C 6F 5)Ph2P

B(C 6F 5)3

H2

[(C 6F 5)Ph2PH] [HB(C 6F 5)3]

cation posseses much greater bronsted acidity

Greb, L.; Ona-Burgos, P.; Schirmer, B.; Grimme, S.; Stephan, D. W.; Paradies, J. ACIE, 2012, 51, 10164-10168.

Hydrogenation of Non-Polar Substrates


Hydrogenation of Olefins

(C 6F 5)Ph2P

B(C 6F 5)3

H2

[(C 6F 5)Ph2PH] [HB(C 6F 5)3]

cation posseses much greater bronsted acidity

Ph

20 mol % (C 6F 5)Ph2P
20 mol % B(C 6F 5)3

Ph
Me

Ph

5 bar H 2, r.t.

Ph

99%

Greb, L.; Ona-Burgos, P.; Schirmer, B.; Grimme, S.; Stephan, D. W.; Paradies, J. ACIE, 2012, 51, 10164-10168.

Hydrogenation of Non-Polar Substrates


Hydrogenation of Olefins

(C 6F 5)Ph2P

H2

B(C 6F 5)3

[(C 6F 5)Ph2PH] [HB(C 6F 5)3]

cation posseses much greater bronsted acidity

Ph

20 mol % (C 6F 5)Ph2P
20 mol % B(C 6F 5)3

Ph
Me

5 bar H 2, r.t.

Ph

Ph

99%
Ph
HB(C 6F 5)3
Me
Ph

Ph N
Ph

Me
Ph

hydride delivery
H HB(C 6F 5)3

69%
Ph
Me

Ph

Ph
NMePh

Ph 2NMe

Friedel Crafts

Ph
Ph
Me

31%

Greb, L.; Ona-Burgos, P.; Schirmer, B.; Grimme, S.; Stephan, D. W.; Paradies, J. ACIE, 2012, 51, 10164-10168.

Hydrogenation of Non-Polar Substrates


Hydrogenation of Olefins
R
R

[(C 6F 5)Ph2PH] [HB(C 6F 5)3]

proton transfer

R
Me

HB(C 6F 5)3

hydride delivery

Me
R

Greb, L.; Ona-Burgos, P.; Schirmer, B.; Grimme, S.; Stephan, D. W.; Paradies, J. ACIE, 2012, 51, 10164-10168.

Hydrogenation of Non-Polar Substrates


Hydrogenation of Olefins
R

[(C 6F 5)Ph2PH] [HB(C 6F 5)3]

proton transfer

Me

R
Me

HB(C 6F 5)3

hydride delivery

Me
R

Me

Me

96%

85%

Greb, L.; Ona-Burgos, P.; Schirmer, B.; Grimme, S.; Stephan, D. W.; Paradies, J. ACIE, 2012, 51, 10164-10168.

Hydrogenation of Non-Polar Substrates


Hydrogenation of Olefins
R

[(C 6F 5)Ph2PH] [HB(C 6F 5)3]

proton transfer

Me

R
Me

HB(C 6F 5)3

Me

Me

96%

hydride delivery

Me
R

Me

MeO

85%

30%

Greb, L.; Ona-Burgos, P.; Schirmer, B.; Grimme, S.; Stephan, D. W.; Paradies, J. ACIE, 2012, 51, 10164-10168.

Hydrogenation of Non-Polar Substrates


Hydrogenation of Olefins
R

[(C 6F 5)Ph2PH] [HB(C 6F 5)3]

proton transfer

Me

R
Me

HB(C 6F 5)3

Me

Me

96%

Me

MeO

85%

hydride delivery

Me
R

Me

Cl

30%

10%

Greb, L.; Ona-Burgos, P.; Schirmer, B.; Grimme, S.; Stephan, D. W.; Paradies, J. ACIE, 2012, 51, 10164-10168.

Hydrogenation of Non-Polar Substrates


Hydrogenation of Olefins
R

[(C 6F 5)Ph2PH] [HB(C 6F 5)3]

proton transfer

Me

R
Me

HB(C 6F 5)3

Me

Me

hydride delivery

Me

Me
Me
TMS

Me

96%

MeO

85%

Cl

30%

10%

95%

Greb, L.; Ona-Burgos, P.; Schirmer, B.; Grimme, S.; Stephan, D. W.; Paradies, J. ACIE, 2012, 51, 10164-10168.

Hydrogenation of Non-Polar Substrates


Hydrogenation of Olefins
R

[(C 6F 5)Ph2PH] [HB(C 6F 5)3]

Me

proton transfer

Me

R
HB(C 6F 5)3

Me

Me

hydride delivery

Me

Me
Me
TMS

Me

96%

MeO

85%

Cl

30%

10%

95%

99%
Me

Me

Me

Me
Me

99%
Greb, L.; Ona-Burgos, P.; Schirmer, B.; Grimme, S.; Stephan, D. W.; Paradies, J. ACIE, 2012, 51, 10164-10168.

Hydrogenation of Non-Polar Substrates


Hydrogenation of Alkynes to Cis-Alkenes

NMe 2
B

C6F 5

R'

NMe 2

H
R'

B
C6F 5

Chernichenko, K.; Madarsz, A.; Ppai, I.; Nieger, M.; Leskela, M.; Repo, T. Nat. Chem., 2013, 5, 718-723.

Hydrogenation of Non-Polar Substrates


Hydrogenation of Alkynes to Cis-Alkenes

R'

NMe 2

NMe 2
B

H
R'

B
C6F 5

C6F 5

Me

Me

H2

N
H H
R'

B
C6F 5 H

Chernichenko, K.; Madarsz, A.; Ppai, I.; Nieger, M.; Leskela, M.; Repo, T. Nat. Chem., 2013, 5, 718-723.

Hydrogenation of Non-Polar Substrates


Hydrogenation of Alkynes to Cis-Alkenes

R'

NMe 2

NMe 2
B

C6F 5

Me

Me
H H

R'
R

H2

R'

C6F 5

R'

B
C6F 5 H

Chernichenko, K.; Madarsz, A.; Ppai, I.; Nieger, M.; Leskela, M.; Repo, T. Nat. Chem., 2013, 5, 718-723.

Hydrogenation of Non-Polar Substrates


Hydrogenation of Alkynes to Cis-Alkenes
NMe 2
C6F 5

C6F 5

R'

H2
Me
N

Me
H F

B
C6F 5 H
F

NMe 2

NMe 2

80 C

H
R'

B
C6F 5

C6F 5

Me

Me

H2

H H

R'
R

R'

B
C6F 5 H

Chernichenko, K.; Madarsz, A.; Ppai, I.; Nieger, M.; Leskela, M.; Repo, T. Nat. Chem., 2013, 5, 718-723.

Hydrogenation of Non-Polar Substrates


Hydrogenation of Alkynes to Cis-Alkenes
NMe 2
C6F 5

C6F 5

R'

H2
Me
N

Me
H F

B
C6F 5 H
F

NMe 2

NMe 2

80 C

R'

B
C6F 5

C6F 5

NMe 2

D2

C6F 5

H
D
Me

Me

H2

H H

R'
R

R'

R'

B
C6F 5 H

Chernichenko, K.; Madarsz, A.; Ppai, I.; Nieger, M.; Leskela, M.; Repo, T. Nat. Chem., 2013, 5, 718-723.

Asymmetric Catalytic Hydrogenation


Hydrogenation of Imines

Me

Me
B(C 6F 5)2

OMe
Me

OMe

Ph

HN

(5 mol %)
Me

Me

tBu 3P (5 mol %)
25 bar H 2

>99%
81% ee

Me

Me C6F 5F
B

Me

H F
N
Ph

Me

favored approach

Me
F

Me F
F

F
F

C6F 5

OMe

H
Me

Me

disfavored approach

Chen, D.; Wang, Y.; Klankermeyer, J. ACIE, 2010, 49, 9475-9578.

Applications in Green Chemistry


Reversible CO 2 Binding

tBu 3P

B(C 6F 5)3

CO2, 25 C

(tBu) 3P

B(C 6F 5)3
O

80 C
vacuum, 5 hrs
-CO2

87%

B(C 6F 5)3
Mes 2P

CO2, 25 C

Mes 2P

B(C 6F 5)3
O

CH2Cl2, > -20 C


-CO2
Mes 2P

B(C 6F 5)3

79%

Mmming, C. M.; Otten, E.; Kehr, G.; Frhlich, R.; Grimme, S.; Stephan, D. W.; Erker, G. ACIE, 2009, 48, 6643-6646.

Applications in Green Chemistry


SO 2 and N 2O Binding
SO2 is a major air pollutant, precursor to acid rain

tBu 3P

B(C 6F 5)3

SO2, 25 C

(tBu) 3P

B(C 6F 5)3
S

80%
B(C 6F 5)3
Mes 2P

SO2, -75 C

Mes 2P

S* O

B(C 6F 5)3

O
Mes 2P

B(C 6F 5)3

83%

Sajid, M. et. al. Chem. Sci., 2013, 4, 213-219.

Applications in Green Chemistry


SO 2 and N 2O Binding
SO2 is a major air pollutant, precursor to acid rain

tBu 3P

B(C 6F 5)3

SO2, 25 C

(tBu) 3P

B(C 6F 5)3
S

80%
B(C 6F 5)3
Mes 2P

SO2, -75 C

Mes 2P

S* O

B(C 6F 5)3

O
Mes 2P

83%

B(C 6F 5)3

N 2O is a minor constituent in the atmosphere, but ~300x more potent as a greenhouse gas

tBu 3P

B(C 6F 5)3

N 2O, 25 C

(tBu) 3P

B(C 6F 5)3

76%

Sajid, M. et. al. Chem. Sci., 2013, 4, 213-219.


Otten, E.; Neu, R. C.; Stephan, D. W. JACS, 2009, 131 , 9918-9919.

Applications in Green Chemistry


Converting CO 2 to Fuels
Addition of Et 3SiH to CO2 in the presence of an FLP efficiently reduces CO2 to CH4

Me

Me
NH 2
Me

HB(C 6F 5)3

Me

Berkefeld, A.; Piers, W. E.; Parvez, M. JACS, 2010, 132 , 10660-10661.

Applications in Green Chemistry


Converting CO 2 to Fuels
Addition of Et 3SiH to CO2 in the presence of an FLP efficiently reduces CO2 to CH4

B(C 6F 5)3
TMPH

O
H

CO2
Me

Me
NH 2
Me

HB(C 6F 5)3

Me

Berkefeld, A.; Piers, W. E.; Parvez, M. JACS, 2010, 132 , 10660-10661.

Applications in Green Chemistry


Converting CO 2 to Fuels
Addition of Et 3SiH to CO2 in the presence of an FLP efficiently reduces CO2 to CH4
Et 3SiH + B(C 6F 5)3

B(C 6F 5)3
TMPH

O
Et 3Si

H
B(C 6F 5)3

CO2
O
O
H

SiEt 3

Me

Me
NH 2
Me

HB(C 6F 5)3

Me

Berkefeld, A.; Piers, W. E.; Parvez, M. JACS, 2010, 132 , 10660-10661.

Applications in Green Chemistry


Converting CO 2 to Fuels
Addition of Et 3SiH to CO2 in the presence of an FLP efficiently reduces CO2 to CH4
Et 3SiH + B(C 6F 5)3

B(C 6F 5)3
TMPH

O
H

Et 3Si

H
B(C 6F 5)3

CO2
O

SiEt 3

O
H

Me

Me
NH 2
Me

Et 3Si

B(C 6F 5)3

B(C 6F 5)3

O
O
Et 3Si

HB(C 6F 5)3

Me

SiEt 3
H

Berkefeld, A.; Piers, W. E.; Parvez, M. JACS, 2010, 132 , 10660-10661.

Applications in Green Chemistry


Converting CO 2 to Fuels
Addition of Et 3SiH to CO2 in the presence of an FLP efficiently reduces CO2 to CH4
Et 3SiH + B(C 6F 5)3

B(C 6F 5)3
TMPH

O
H

Et 3Si

H
B(C 6F 5)3

CO2
O

SiEt 3

Me

Me

NH 2
Me

Et 3Si

O
O
Et 3Si

Me

B(C 6F 5)3

B(C 6F 5)3

SiEt 3

HB(C 6F 5)3

Et 3Si

B(C 6F 5)3

H
Et 3Si

H
H

(Et 3Si)2O
+ B(C 6F 5)3
Berkefeld, A.; Piers, W. E.; Parvez, M. JACS, 2010, 132 , 10660-10661.

Applications in Green Chemistry


Converting CO 2 to Fuels
Addition of Et 3SiH to CO2 in the presence of an FLP efficiently reduces CO2 to CH4
Et 3SiH + B(C 6F 5)3

B(C 6F 5)3
TMPH

O
H

Et 3Si

H
B(C 6F 5)3

CO2
O

SiEt 3

Me

Me

NH 2
Me

Et 3Si

O
O
Et 3Si

Me

B(C 6F 5)3

B(C 6F 5)3

SiEt 3

HB(C 6F 5)3

Et 3Si

B(C 6F 5)3

H
Et 3Si

H
(Et 3Si)2O
+ B(C 6F 5)3

Et 3Si

B(C 6F 5)3

HCH 3

H
(Et 3Si)2O
+ B(C 6F 5)3

Berkefeld, A.; Piers, W. E.; Parvez, M. JACS, 2010, 132 , 10660-10661.

Limitations and Future Directions

Currently cannot hydrogenate aldehydes or ketones catalytically


O
H
Me
Me

N
H2

Me
Me

HB(C 6F 5)3

Me

20 C, 1hr

Me

N
H2

Me

B(C 6F 5)3

Me

95%

Discovery of better FLP catalysts for asymmetric induction; expanding the scope
to olefin hydrogenations

Hydrogen gas storage - currently FLPs can achieve 0.25 wt % H 2; whereas to be practical
need 6 - 9 wt % H 2 (i.e. ammonia-borane)

Sumerin, V.; Schulz, F.; Nieger, M.; Leskel, M.; Repo, T.; Rieger, B. ACIE, 2008, 47, 6001-6003.

Summary
I. Theories on the Mechanism of H 2 Activation
Electron Transfer Model that Invokes Frontier Molecular Orbitals
Electric Field Model that disregards Frontier Molecular Orbitals
Secondary non-covalent interactions play key role in lowering H 2 activation barrier

II. Applications of FLPs in Hydrogenation Reactions and Storage of Small Molecules


Catalytic hydrogenation of imines, enamines, nitriles, aziridines, silyl enol ethers,
cyclic ethers, alkenes, alkynes, ynones
Stoichiometric hydrogenations of aldehydes, ketones
Asymmetric imine hydrogenations
Advances in area of green chemistry