, ! . e 4 ?O

, , ! ! . . e e 4 4 ? ?O O

Prof. Simon Aldridge Oxford University

Postdoc

w. Thomas Fehlner (U Notre Dame) w. Michael Mingos (Imperial Col. London) Ph.D. in 1996

w. Anthony Downs@Oxford U Graduated Oxford U

[V]bG TOC Ya_U\X?O3LRQAG

d`cZcI C–C /J#*H d Al T^Wc$S)>E>Q

d"F`cZcI C–C /S6*H

Abstract: The activation of C–C bonds is of fundamental interest in the

construction of complex molecules from petrochemical feedstocks. In the case of the archetypal aromatic hydrocarbon benzene, C–C cleavage is

thermodynamically disfavored, and is brought about only by transient highly reactive species generated in situ. Here we show that the oxidative addition of the C–C bond in benzene by an isolated metal complex is not only possible, but occurs at room temperature and reversibly at a single aluminium center in [(NON)Al]− (where NON = 4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9- dimethylxanthene). Selectivity over C–H bond activation is achieved kinetically and allows for the generation of functionalized acyclic products from benzene.

Abstract ?OBOH3LRQAG

dARKFH<+S)>E`cZcI C–C =P

d:CD Al T^WcHCE"F6*H C–C I9*@82 d74*H C–H /NPM C–C @

%50 - 6

d`cZc?O1BRD;'&$@(

Hicks, J.; Vasko, P.; Goicoechea, J. M.; Aldridge, S.

Reversible, Room-Temperature C–C Bond Activation of Benzene by an Isolable Metal Complex.

J. Am. Chem. Soc. 2019, 141, 11000-11003.

Prof. Jose Goicoechea Oxford University

Postdoc

w. Slavi C. Sevov (U Notre Dame) Ph.D. in 2003

w. Michael K. Whittlesey@U of Bath

Graduated U de Zaragoza

Introduction:  „ „z z„ „g gb bV Vc c† † „ „z z„ „h h C-H = = & &

w„|ƒuHmRh03

(1) A%5i;H\fZcoCVhdU^h abstract e>`[doDc2su"n (2) lela_*p?G (review) ih|}{xgQ]rfhX`[tXsjCV

Ref 1 i„z„h<gbVchI%

Ref 2 i„z„h+KgbVchI%

Ref 3 iM +KgTNu!b4g aromatic eVW

7Func7V_I%

Ref 4 i 1-3 hI%^hu7\fYq

„z„h+Kh-ulen_I%

Ref 5: ),h$9(‡

„z„i.S@#d^h+Kub Ref 6: L:O π v‚…„PgbVch*

Ref 7: ),Oh*ˆ„z„hB~ƒ|„YEJ

Ref 8

Cp

2

W Pg]r

„z„ C-H =hN8

Ref 9: C-H 1gbVch?G

%5h6CV '/

'kyxƒ…\c%5€y|k

Introduction 2: C-C

Ref 10 Ref 14

Ref 11: Ref 10 (Nature ) Ref 12

C-C

W PMe₃

Me₃P Me₃P

PMe₃ C N C N W

PMe₃ CH2

PMe₂ Me₃P

Me₃P PMe₃

H N

N QoxH

Ref 13

!#$ C-C

Si(II) "$ $ C-C

Ref 15

P(I) "$ $ C-C

Ref 16

Ru p-cymene C-C %

Introduction 3: C-C

Ref 17

Cp′

Cp′

Cp′Ti Ti

Ti HH

HH HH H

1

40 °C, 36 h –H₂

H

H H

H H

H

2, quantitative

Ti Ti

H Ti H H

H CH₃ H H

H H Cp′

Cp′

Cp′

Ti(III)

2

Ti(IV) "-0(0 C-C

Ref 18

Pd(II) "-0(0

C-C

Ref 19

Ir(I) "-0(0 C-C

Ref 20

'#)$*/ "+/$0 C-C ( !%/-0 )

R

NjCH COjAlk

IAik DA) 2

Ref 21a

'#)#/&/ "-0(0

C-C (Rh(II) !%/-0 )

Ref 21b

'#.,%/-0 "-0(0 C-C ( !%/-0 )

Ref 22

Si(II) "-0(0

C-C

Ref 23

Si(II) "-0(0

C-C

= Buchner ring expansion

Introduction 4: Al ! !* *# #2 2

   

 

 

   

 

 

(i) K[N(SiMe3)2] (ii) AlI3

KC8 (excess)

(NON)H₂ [Al(NON)]₂

[K{Al(NON)}]₂ KC8 (1 equiv.)

(NON)AlI O

tBu

tBu

NH Dipp NH

Dipp

O

tBu

tBu

N Dipp N

Dipp

Al I

O

tBu

tBu

N Dipp N

Dipp

Al O

tBu

tBu

N Dipp

N Dipp

Al

O

tBu

tBu

N Dipp N

Dipp

Al O

tBu

tBu

N Dipp

N Dipp

Al K

K

Ref 24

 

 

 

(NON)AlMe [K{Al(NON)}]₂

MeOTf or MeI

(NON)AlH

(Nacnac)^MesMgAl(NON) (NON)Al Al(NON)

(NON)AlI HX / –KX

[K{H₂Al(NON)}]₂ (R = H)

H2 or C6H6

[K{Ph(H)Al(NON)}]₂ (R = Ph)

(Nacnac)^MesMgI(OEt2) –KOTf or KI O

tBu

tBu

N Dipp N

Dipp

Al H

O

tBu

tBu

N Dipp N

Dipp

Al O

tBu

tBu

N Dipp

N Dipp

Al K

K

O

tBu

tBu

N Dipp N

Dipp

Al Me

O

tBu

tBu

N Dipp N

Dipp

Al Mg

H H R

R

N N

Mes Mes [e.g. (NON)H2

–K2(NON)]

Al !*#20"& 3

Ref 25

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

O

tBu

tBu

N

N Dipp

Dipp

Al O

tBu

tBu

N N

Dipp Al Dipp K

K

O

tBu

tBu

N

N Dipp

Dipp Al Au P^tBu3

1 3

tBu3PAuI

– KI

  �

    �  

 

   

 

 

 

 

 

   

   

 

 

 

 

   

   

   

 

 

 

 

 

 

 

 

 

 

 

O

tBu

tBu

N

N Dipp

Dipp Al

E E iPrNCNⁱPr

or CO₂

Au P^tBu3

E =ⁱPrN, 4 E = O, 5

� �

Al !*#2(/2&.'0 $0,%"-) CO

2

Al !*#2

Al-I

+1(2

Al–Al

S

N

2

C–H, H–H (/2&.'0

This Work 1: F FH HE ER RL LO OS S< < Al D DJ JE ER R

Al–N 2.022(1) Å 2.049(1) Å Al–O 2.175(1) Å

Scheme 1. Sequestration of the Potassium Cations from Dimeric 1 To Generate Monomeric Aluminyl Compound [K(2.2.2-crypt)][(NON)Al], 2

Scheme 2. Room Temperature C  C Bond Activation of Benzene by 2 To Give Metallacycle 3; Facile Exchange of the C

₆

H

₆

Fragment of 3 in the Presence of C

₆

D

₆

Al–N 1.963(2) Å 1.956(2) Å Al–O 2.279(2) Å

Cf. 1 =NRGR9 60 ℃, 96 +837 Al(H)(Ph) #C"5B

d

_H

7.21, 7.00, 5.97 ppm Crystal structure of 3

Crystal structure of 2

Al–C 1.980(2) Å C–C 1.343(2) Å 1.442(3) Å 1.352(3) Å 1.451(3) Å 1.352(3) Å

<KJP Al 9

;(

Temperature (°C) Rate constant (k)

60 2.31 x 10^–5

65 4.53 x 10^–5

70 8.73 x 10^–5

75 1.639 x 10^–4

80 2.759 x 10^–4

Al···Al 0@> Al···K = ;*. (>7 Å)

3 ;37 C

6

D

6

C- 3 < ;/

Al T!<MQIR< C

1

H NMR 8'&37)C$

Scheme 3. Reactions of 2 and 3 with Naphthalene at 80 °C To Give a Mixture of C  H Activation Products Resulting from Attack at the 1 and 2 Positions

²⁹

LOSDJER 2 0@>NRGR 3 <:6A1A?

48 4a,4b 2" →3 1A<NRGR<%,C

This Work 2: + +5 5O O( (3 3

Figure 2. DFT-calculated (DFT-D3, PBE0, Def-TZVP) pathways for benzene CC and CH bond activation by 2′. For computational efficiency the backbone^tBu groups of the NON ligand were replaced by methyl groups in all calculations. The“cut-down”versions of compounds 2,3and5so modeled are labeled2′,3′and5′.

t

Bu Y Me N'$

&NP C–C ," 3’ TVS C–H " 5’ C IC

3’ QO TS P 23 kJ/mol @OK 64&NP 3’ O"C

3’ BU 5’ QP 137 kJ/mol MOK

%.IL-AUXW

→ ?&N 3 Y 80 ℃ K:<GWL 5 C"GWC*P0=MLMV NON 8O1S(3EXW

DFT 2)KP 2’ BU 3’ QP< Int Y+#

Int P 2’ Lag]gO (1+2) !LRMHW

→ ?&NP 2 LZ_fgCFJ 9&N 6 YAW (C–C 1.598(2) Å)

6

5

< Int BU 3’ QP 6π >! K

;!C7/GWL-AUXW

Scheme 4. Generation of an Acyclic Product Containing a

cis,cis,cis

Triene Fragment by the Reaction of 3 with a Tin Electrophile

[\Q`cg[b^eGWDLK

cis,cis,cis `dZgC"

Other Experiments and Next Approach

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