Electrophile-Induced Disproportionation of the Neutral Formyl (Î·

10 Electrophile-Induced Disproportionation of the Neutral Formyl (η-C H )Re(NO)(PPh )(CHO) 5

5

3

Isolation and Properties of the Rhenium Methylidene [(η-C5M5)Re(NO)(PPh )(CH )] PF +

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J. A. GLADYSZ, WILLIAM A. KIEL, GONG-YU LIN, WAI-KWOK WONG, and WILSON ΤΑΜ Department of Chemistry, University of California, Los Angeles, CA 90024 A variety of organic molecules (methane, methanol, higher a l kanes and alcohols, glycols, gasoline hydrocarbons) can be ob tained from CO/H gas mixtures (synthesis gas) in the presence of metallic heterogeneous and homogeneous catalysts [1,2]. Since synthesis gas can be readily produced from coal, and domestic crude oil and natural gas reserves (conventional sources of the aforementioned organic chemicals) are declining, there is intense current interest in CO/H chemistry. Research in numerous labora tories is being directed toward the development of milder and/or more selective CO reduction catalysts, and the delineation of CO reduction mechanisms (see other papers contributed to this symposi um, and leading references [3-9]). In considering the formative stages of CO reduction, one is struck by the fact that only a finite number of single carbon cata lyst-bound intermediates is possible. Candidate intermediates for which some type of experimental support exists are given in Figure 1 [1,2]. On the basis of available data, i t is most probable that more than one distinct mode of CO reduction (and homologation to C and higher intermediates) can occur. 2

2

2

I t i s not at t h i s time p r a c t i c a l to probe the f i n e r d e t a i l s of CO reduction using the a c t u a l c a t a l y s t s employed to e f f e c t C0/H r e a c t i o n s . Reaction c o n d i t i o n s are severe and many i n t e r mediates are expected to l i e i n r e l a t i v e l y shallow p o t e n t i a l energy w e l l s . We t h e r e f o r e i n i t i a t e d a program aimed at s y n t h e s i z i n g s t a b l e homogeneous t r a n s i t i o n metal complexes c o n t a i n i n g l i g a n d s corresponding to the c a t a l y s t - b o u n d intermediates i n Figure 1 [1018]. Through i n v e s t i g a t i o n of t h e i r b a s i c chemistry, we have sought to gain i n s i g h t i n t o p o s s i b l e c a t a l y s t r e a c t i o n pathways. Considerable challenge i s a s s o c i a t e d w i t h s y n t h e s i z i n g s t a b l e complexes c o n t a i n i n g c e r t a i n o f the l i g a n d s shown i n Figure 1. Although t r a n s i t i o n metal-CO and t r a n s i t i o n metal-CH complexes have long been known, t r a n s i t i o n metal complexes c o n t a i n i n g the other s i x l i g a n d types i n Figure 1 were unknown p r i o r to the e a r l y 2

3

oo97-6feBeric8ibi:heiBifialo() 0

©

1 9 8 1

^S«ftii

SÊ?HJftifY

S o c i e t

y

1155 16th St. N. W. Ford; Catalytic Activation of Carbon Monoxide 0. C. 20036 ACS Symposium Series;Washington, American Chemical Society: Washington, DC, 1981.

CATALYTIC ACTIVATION OF CARBON MONOXIDE

148

1970's [1_,2]. In a l l c a s e s , r a t i o n a l i z a t i o n s can be advanced as t o why kTnetic i n s t a b i l i t y i s a n t i c i p a t e d . Other research groups have a c t i v e l y pursued s i m i l a r l i n e s of r e s e a r c h , and t h e i r important c o n t r i b u t i o n s ( s t u d i e s by Casey and Graham are p a r t i c u l a r l y r e l e v a n t : [ 1 9 , 2 0 , 21J) w i l l be reviewed more thoroughly i n our f u l l papers. In t h i s Symposium account, we s h a l l describe the use o f c a t i o n s [ ( n - C H ) R e ( N 0 ) ( C 0 ) ] BF,»" (1) [22] and [ ( n - C H ) R e ( N 0 ) ( P P h ) ( C 0 ) ] BFi»" (2a) as precursors to~a number o f complexes c o n t a i n i n g l i g a n d s of the types i n Figure 1. We chanced upon these systems i n the course o f prospecting f o r s t a b l e neutral formyl complexes [ 1 5 ] . E a r l i e r , we had found t h a t [ ( n - C H ) M n ( N 0 ) ( C 0 ) ] P F " reacted with L i ( C H ) B H to a f f o r d the manganese formyl (n-C H )Mn(N0)(CO)(CHO),which r a p i d l y decomposed at 10 °C [ 1 5 ] . Based upon abundant precedent [ 1 2 ] , i t seemed probable t h a t rhenium homologs would have greater k i n e t i c s t a b i l i ty. We were a l s o i n f l u e n c e d by Graham's i n t r i g u i n g 1972 report t h a t NaBH* reduced 1 to the methyl complex (n-C H )Re(N0)(C0)(CH ) (3) [ 2 0 ] . As w i l l Be r e l a t e d , the same metal/ligand arrangements wKich a f f o r d k i n e t i c a l l y s t a b l e n e u t r a l formyls have been found to s t a b i l i z e other r e a c t i v e l i g a n d types as w e l l . 5

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3

Results and D i s c u s s i o n Rhenium c a t i o n s 1 and 2a are synthesized by the convenient procedures shown i n Figure 27 The use of iodosobenzene ( C H 5 l - 0 ~ ) in the conversion of 1 t o 2a m e r i t s note. S u b s t i t u t i o n of Ph P f o r a CO i n 1 could not be~effected by standard thermal or photochemical metfiodSo Furthermore, r e a c t i o n of 1 with (CH ) N -0~ (which i s commonly used f o r the o x i d a t i v e removal of metal-bound CO) [12] i n the presence o f Ph P d i d not y i e l d any CO-containing p r o d u c t s . Consequently a more s e l e c t i v e reagent f o r the o x i d a t i o n of l i g a t i n g CO to C0 was sought. A f t e r surveying several p o s s i b i l i t i e s , i t was found that the r e a c t i o n of 1 i n CH CN with commerc i a l l y a v a i l a b l e iodosobenzene r e s u l t e d i n ' t h e smooth formation of [(n-C5H )Re(N0)(C0)(NCCH )] B F ^ . As would be expected from a r e a c t i o n i n v o l v i n g a t t a c k o f iodosobenzene oxygen upon CO, i o d o benzene ( C H I ) was formed i n 77% GLC y i e l d . The [ ( n - C H ) R i T N 0 ) (C0)(NCCH )] BFit" could be p u r i f i e d o r simply r e f l u x e d i n crude form with Ph P i n 2-butanone ( s u b s t i t u t i o n was slow i n r e f l u x i n g acetone) to a f f o r d 2a i n 50-65% o v e r a l l y i e l d . _ _, The r e a c t i o n of"! w i t h L i ( C H ) B H was i n v e s t i g a t e d f i r s t [15]. As shown i n Figure 3 , the r e l a t i v e l y s t a b l e n e u t r a l formyl (n-C H )Re(N0)(C0)(CH0) (4) formed i n q u a n t i t a t i v e s p e c t r o s c o p i c y i e l d . 4 decomposed over'several hours at room temperature, and we were unable t o i s o l a t e 4 i n a n a l y t i c a l l y pure form. Similar syntheses and o b s e r v a t i o n s ' ^ r e a l s o reported by Casey [19] and Graham [21_]. Despite i t s i n s t a b i l i t y , r e a c t i o n s of 4 with reducing agents were i n v e s t i g a t e d (Figure 4 j [ 1 5 ] . Importantly, BH *THF smoothly reduced formyl 4 to methyl 3 . This suggests t h a t 4 (or a BH +

6

3

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Ford; Catalytic Activation of Carbon Monoxide ACS Symposium Series; American Chemical Society: Washington, DC, 1981.

GLADYSZ

ET

AL.

Disproportionation of Neutral Formyl

Figure 2. Synthesis of starting metal car bony I cations


149

150


Li(C H ) BH 2

5

3

"Υ"» CO

spectroscopic yield

]

1 3

ON^f-CO C \ 0 v

H NMR: δ 15.77

C NMR: 265.9, 200.1, 96.8 (-60 ° C , THF-dg)

IR:

1985 s , 1709 s , 1614 s (THF, cm " ) Ί

Figure 3.

I

/Re\ ON H

2

Λ relatively stable neutral formyl complex

BH--THF

/Re\ ON I CO

CO

CH

O

76% 3

3

^ι(ε Η ) ΒΗ 2

5

3

150 psi

no reaction

ON

I C

H ' %

Figure 4.

Cv

80% 0

5

Reductions of "semi-stable" formyl 4


10.

GLADYSZ ET AL.

151


adduct) i s an intermediate i n Graham's NaBHi» reduction of 1 to 3, I n t e r e s t i n g l y , r e a c t i o n o f 4 with L i ( C H ) 3 B H afforded the~anionic b i s - f o r m y l Li [(n-C H )Re(N0y(CH0) ]" ( 5 ) , derived from attack at the remaining CO o f 4 . This species had a h a l f l i f e of c a . 2 hr at room temperature. It i s s i g n i f i c a n t t h a t the e l e c t r o p h i l i c r e ductant BH a t t a c k s the formyl l i g a n d of 4 , whereas the n u c l e o p h i l i c reductant L i ( C H ) 3 B H a t t a c k s the carbonyl l i g a n d of 4. P r e v i ously i t has been noted that e l e c t r o p h i l e s such as L i bind much more e f f e c t i v e l y to acyl l i g a n d s than carbonyl l i g a n d s [ 1 3 ] , where as n u c l e o p h i l e s p r e f e r e n t i a l l y a t t a c k the carbonyl l i g a n d s i n metal [25] carbonyl a c y l s [11,26]. Formyl 4 d i d not r e a c t with 150 p s i of H at a r a t e d e t e c t a b l y f a s t e r than Tts decomposition, and we considered i t u n l i k e l y t h a t the other reductions i n Figure 4 had an important bearing on the f a t e o f c a t a l y s t - b o u n d f o r m y l s . Moreover, we sought a c r y s t a l l i n e , a n a l y t i c a l l y pure neutral formyl complex whose p h y s i c a l and chemi cal p r o p e r t i e s could be subjected to unambiguous d e f i n i t i o n . To ward t h i s end, the P h P - s u b s t i t u t e d c a t i o n 2a would provide a more e l e c t r o n r i c h rhenium system whose a d d i t i o n a l phenyl r i n g s might impart greater c r y s t a l u n i t y . G r a t i f y i n g l y , r e a c t i o n of 2a with Li(C H )3BH afforded the s t a b l e (dec p t . c a . 91 °C) formyl (r,-C H )Re(N0)(PPh )(CH0) ( 6 ) , which c o u l d be i s o l a t e d i n c r y s t a l l i n e a n a l y t i c a l l y pure form (60% y i e l d ) a f t e r column chromatography (Figure 5 ) [ 1 5 ] . L a t e r , we found that the r e a c t i o n o f NaBf-U with 2a i n THF/H 0 afforded 55-75% y i e l d s of 6. This formyl was suBjected to an X-ray c r y s t a l s t r u c ture determination [ 1 6 ] , a s t e r e o s c o p i c view of which i s given i n Figure 6. While the c h a r a c t e r i s t i c s p e c t r o s c o p i c f e a t u r e s of f o r myl complexes have been p r e v i o u s l y noted [ 1 0 , 1 1 , 1 2 , 1 3 , 1 9 , 2 1 ] , i t should be emphasized t h a t the low frequency formyl IR s t r e t c h o f 6 (1566 cm" in THF) i n d i c a t e s a s u b s t a n t i a l resonance c o n t r i b u t i o n from the d i p o l a r carbenoid form 6b. I n t e r e s t i n g l y , the plane of the formyl l i g a n d v i r t u a l l y e c l i p s e s the Re-N-0 p l a n e ; an i d e n t i c a l geometric r e l a t i o n s h i p i s observed i n the X-ray c r y s t a l s t r u c t u r e s of homologous c a t i o n i c rhenium a l k y l i d e n e complexes [ 2 7 ] . Enhanced s t a b i l i t y i s often detrimental to r e a c t i v i t y , and i t came as no s u r p r i s e t h a t 6 d i d not r e a c t with 150 p s i of H at 25 °C. When reacted with BH^-THF, 6 was reduced t o (n-C H )Re(N0)(PPh )(CH ) (7) (eq i ) . Methyl complex 7 could a l s o be obtained by reduction of 2 with NaBHi*. However, s i n c e the prospects f o r r e duction chemistry relevant t o the f a t e o f c a t a l y s t - b o u n d formyls seemed b l e a k , we began t o i n v e s t i g a t e other f a c e t s of the chemistry of β. Our i n i t i a l experiment along these l i n e s was a w e l l - p r e c e d e n t ed attempt to 0-methylate the formyl l i g a n d i n § . Considering the seemingly u n e x c i t i n g products shown i n Figure 7, I was very g r a t e f u l t h a t my co-workers were s u f f i c i e n t l y curious not to r e l e g a t e t h i s r e a c t i o n to the rhenium waste j a r . Upon f u r t h e r thought, we speculated t h a t the products 7 and 2b (Figure 7) might c o n s t i t u t e formyl reduction and o x i d a t i o n p r o d u c t s , r e s p e c t i v e l y . Therefore 2

+

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1

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3



Li(C H ) BH 2

/ PPho

ON CO 2a

Found:

60%

ON H

0

C, 50.34; H, 3,70; N, 2.45, P, 5.41 C, 50.14; H, 3.82; N, 2.39; P, 5.34

IR (cm" , THF):

1663 s , 1566 s ;

H NMR (CgDg, δ ) : 17.23

1 3

Figure 5.

^

55-75%

1

]

3

NaBH,

BFy,

Anal. Calcd:

5

C NMR (-60 ° C , THF-dg):

246.8 ppm.

An isolable, crystalline neutral formyl complex


10.

GLADYSZ

E T

153

Disproportionatioti of Neutral Formyl

AL.

the o r i g i n of the methyl l i g a n d was probed by conducting the same r e a c t i o n w i t h CD S0 F (Figure 8 ) . As shown, the 7 produced was v i r t u a l l y e n t i r e l y Z - d . Thus the methyl l i g a n d 3 i d not a r i s e from the methylating agent, which s t r o n g l y suggested t h a t some type o f d i s p r o p o r t i o n a t e o n was o c c u r r i n g . Remarkably, the formyl l i g a n d was being reduced w e l l below room temperature, and without the a d d i t i o n of an exogenous reducing agent. Formyl 6 was s i m i l a r l y reacted w i t h e l e c t r o p h i l e s ( C H ) S i C l (Figure 9) and CF C0 H (Figure 10). In both c a s e s , methyl com plex 7 and [ ( n - C H ) R e ( N 0 ) ( P P h ) ( C 0 ) ] s a l t s formed i n r a t i o s reasonably c l o s e to 1 : 2 . The r e a c t i o n of β with ( C H ) S i C l a l s o y i e l d e d [ ( C H ) S i ] 0 (approximately equimolar with 7 ) , which we (postulated to c o n t a i n oxygen o r i g i n a l l y from the formyl l i g a n d . H NMR monitored r e a c t i o n s of 6 with CH S0 F i n CD C1 showed the presence of s i m i l a r q u a n t i t i e s ' o f dimethyl e t h e r . In f o r m u l a t i n g means of u n r a v e l i n g the mechanisms of the r e a c t i o n s i n Figures 8-11, we decided to concentrate on the CH S0 F induced d i s p r o p o r t i o n a t i o n , s i n c e e x p l o r a t o r y NMR experiments had shown i t to be somewhat slower than the o t h e r s . We considered the l i g a n d types shown i n eq i i (formyl , methoxymethylidene, methoxymethyl, methylidene, methyl) to represent a l i k e l y r e a c t i o n s e quence. These have c l o s e r e l a t i o n s h i p s with several of the poten t i a l c a t a l y s t - b o u n d intermediates i n Figure 1. The ( C H ) S i C l and CF3CO2H induced d i s p r o p o r t i o n a t i o n s of 6 might i n v o l v e - 0 S i ( C H ) and -OH homologs of the -0CH c o n t a i n i n g l i g a n d s i n eq i i . A three-stage approach was taken to e s t a b l i s h mechanism. F i r s t , e f f o r t s were d i r e c t e d a t the s y n t h e s i s and i s o l a t i o n o f a l l p o t e n t i a l intermediates i n the CH S0 F r e a c t i o n . Secondly, expe riments were conducted t o t e s t the chemical v i a b i l i t y of these i n t e r m e d i a t e s . For i n s t a n c e , s i n c e no external reducing agents are added, some o f the s p e c i e s i n eq i i must be hydride donors, whereas others must be hydride a c c e p t o r s . T h i r d l y , a f t e r i s o l a t i n g a u t h e n t i c samples o f a l l l i k e l y i n t e r m e d i a t e s , i t would be p o s s i ble to c o n v i n c i n g l y i n t e r p r e t the H NMR monitored r e a c t i o n of 6 with C H S 0 F , i n which numerous t r a n s i e n t resonances were observed. In s y n t h e s i z i n g the p o t e n t i a l i n t e r m e d i a t e s , we worked from r i g h t to l e f t through the l i g a n d types shown i n eq i i , as d e t a i l e d i n the remainder of t h i s account [ 1 7 ] . Reaction of 3 with P h C P F " r e s u l t e d i n the formation of methylidene complex [ ( n - C H ) R e ( N 0 ) ( P P h ) ( C H ) ] P F " (8) i n 8 8 100% s p e c t r o s c o p i c y i e l d s , as shown i n Figure 11. Although 8 de composes i n s o l u t i o n s l o w l y at -10 °C and r a p i d l y a t 25 °C (the decomposition i s second order i n 8 ) , i t can be i s o l a t e d as an o f f white powder (pure by H NMR) when the r e a c t i o n i s worked up a t -23 ° C . The methylidene H and C NMR chemical s h i f t s are s i m i l a r t o those observed p r e v i o u s l y f o r carbene complexes [ 2 8 ] . How e v e r , the m u l t i p l i c i t y o f the H NMR spectrum i n d i c a t e s the two methylidene protons t o be non-equivalent (Figure 11). Since no coalescence i s observed below the decomposition p o i n t of 8 , a low e r l i m i t of Δ 6 * >15 kcal/mol can be set f o r the r o t a t i o n a l b a r r i e r about the rhenium-methylidene bond. 3

3

0

3

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+

3

3

3

3

3

2

3

2

3

3

2

2

3

3

3

3

3

3

3

3

1

3

3

+

3

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6

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2

+

6

l

1 3

l

1


3

CATALYTIC

154

(i)

BH3'THF

Je^ ON

PPh

I

ACTIVATION

CARBON

HaBfy

J ON^ I ^ P P h 3

3

OF

^ ON

+7^84%

3

C H

MONOXIDE

+

| >Ph C

3

0

BF

4

2a

'«SSB-

0 ON'

I '

-jKô7—L I™

>Ph3

j H

w

a

r

»

Φ

/ ON

m

η ^0

R

e

I

v I PPh~

/ ON

+

small amounts of a third organometallic product in some experiments

φ R

e

'

3

I

\

+

PPh3

3

7

6

2b

29% isolated

S 0

3

F

56% isolated

Figure 7. Reaction of formyl 6 with CH S0 F s

1.0 equiv CD^SO.F 3 3 ^ I

0 N

H

P P h

^0

^

-78 *warm C , then*

3

R

»

\

e

•+ ^Re^

+

CH. | PPh

ON

3

3

0N^ CO | PPh x

3

3

S0 F3

2b Re-CH : Re-CD 3

Figure 8.

3

Η

j X

PPh N

N

0

3

3

CD C1 2

2

ON

w

1

PPh

CH

-78°C, then warm

>99.9 :

0.1

Origin of Rh-bound methyl

1.0 equiv (CH ) SiCl ON

3

3

3

+

ON

1 CO CI

0

22% 7

"19%"

56% 2c (spectroscopic yields)

Figure 9.

(CH )jSiCl induced formyl disproportionation 3


G L A D Y S Z

E T

Disproporîionation

A L .

1.0 equiv CF~C0 H

ΡΩ

'

9

j PPh

ON

x

CD C1

3

2

N

-78°C, then warm

/Cv H 0 x

J +

| PPh

ON

w

2

155

of Neutral Formyl

| PPh

ON

3

N

CH.

CO

CF C0 "

J

3

28%

72%

7

2d

6

3

2

(spectroscopic yields)

Figure 10.

CF, C0 H induced formyl disproportionation t

Ph.C R

e

/ ,I xPPh ON nN

pph

3

2

-nr

PF ~

+

CD,Cl,. -70'C» 2 2

8 8

o^ïvppu

ON

%

H

PPh

y

/ C ,

H

8

3

1 3

C

Figure 11.

15.67

(t,

15.42

(br d, J _ < = 4, J , _ < 1 Hz)

5

%

J _ « = J _ = 4 Hz) H

H

H

H

p

H

H

p

NMR, gated decoupled: 290.3 ppm, t, J _ = 151 Hz C

H

Synthesis of first detectable electrophilic methylidene complex

/ 0

Re-C

1 0 0 %

isolated

b

Ή NMR:

-

spectrospic;

3

Re =C

CH

3

0CH~

I 3

Re-C-H

I

+

Re =C

H


Re-CH,

156

CATALYTIC

ACTIVATION

OF

CARBON

MONOXIDE

The methylidene complex 8 forms c r y s t a l l i n e , a n a l y t i c a l l y pure adducts with p y r i d i n e and phosphines, as shown i n Figure 12. These r e a c t i o n s e s t a b l i s h the methylidene carbon as e l e c t r o p h i l i c . Relevant to a f u t u r e mechanistic p o i n t , no r e a c t i o n was observed between 8 and dimethyl e t h e r . At the time t h i s work was r e p o r t e d , only one other w e l l - c h a r a c t e r i z e d non-bridging methylidene complex, Schrock*s ( n - C H ) T a ( C H ) ( C H ) [ 2 9 ] , had been d e s c r i b e d i n the l i t e r a t u r e . However, the methylidene carbon i n t h i s complex i s n u c l e o p h i l i c , and undergoes ready r e a c t i o n with ( C H ) S i B r and C D I . L i k e ( n - C H ) 2 T a ( C H ) ( C H ) , 8 t h e r m a l l y decomposes ( i n up t o 50% y i e l d ) to an o l e f i n c o m p l e x r [ ( n - C H ) R e ( N 0 ) ( P P h ) ( H C = C H 2 ) ] P F - . Since c a t a l y s t - b o u n d methylidenes (or higher a l k y l i d e n e homologs) have been suggested to p l a y important r o l e s i n o l e f i n m e t a t h e s i s , o l e f i n c y c l o p r o p a n a t i o n , and Z i e g l e r - N a t t a p o l y m e r i z a t i o n , our s t u d i e s of 8 are c o n t i n u i n g . More r e c e n t l y , a d d i t i o n a l examples of m e t h y l i dene complexes have been reported by Brookhart and Flood [30] and Schwartz [ 3 1 ] . At t h i s s t a g e , i t must be asked whether or not 8 i s a chemic a l l y v i a b l e intermediate i n the formyl d i s p r o p o r t i o n s . To be s o , i t must be able to a b s t r a c t hydride from other organorhenium spec i e s known to be present. A c c o r d i n g l y , when 6 and 8 were mixed i n C D C l a t -70 °C i n a H NMR monitored r e a c t i o n , the~clean hydride t r a n s f e r d e p i c t e d i n eq i i i occurred immediately ( i . e . , w i t h i n the c a . 2-3 minute l a g time needed t o resume sample spinning and a c q u i r e the FT NMR d a t a ) . A t t e n t i o n was next d i r e c t e d at preparing the methoxymethyl complex (n-C H )Re(N0)(PPh )(CH 0CH ) ( 9 ) . Two h i g h - y i e l d routes were developed, as shown i n Figure 13; the synthesis from § i s s l i g h t l y more demanding e x p e r i m e n t a l l y , s i n c e 8 and 2 react r a p i d l y w i t h each other a t -70 °C (vide i n f r a ) . I f 9 i s t o be an intermediate i n the CH S0 F induced formyl d i s p r o p o r t i o n a t i o n of 6 , i t should r e a c t with CH S0 F under the c o n d i t i o n s of the d i s p r o p o r t i o n a t i o n . T h i s would l o g i c a l l y l e a d t o dimethyl e t h e r , an observed product, and methylidene 8 (S0 F" s a l t ) . However, under a v a r i e t y o f c o n d i t i o n s , the r e a c t i o n of 9 w i t h CH S0 F d i d not y i e l d any d e t e c t a b l e 8 (S0 F" s a l t ) , although the formation of dimethyl ether was always~observed. An e a s i e r to i n t e r p r e t , " h a l f - m e t h y l a t i o n " experiment, which r e s u l t e d i n the formation of ca_. 1:1:1 r a t i o of 10a, 7, and dimethyl e t h e r , i s shown i n Figure 14. The r e a c t i o n i n Figure 14 i s more r e a d i l y understood when i t i s noted t h a t 10a i s an o x i d a t i o n product (H~ l o s s from 9 ) , whereas 7 i s a reduction product (formal H" a t t a c k upon 9 ) This suggests t h a t CH S0 F i n i t i a l l y converts 9 to 8 ( S 0 F " ~ s a l t ) , which then r a p i d l y back r e a c t s with 9 to form the'observed products. This can be e a s i l y t e s t e d by simply r e a c t i n g 8 and 9 i n the *H NMR monitored r e a c t i o n shown i n Figure 15. Indeed, hydride t r a n s f e r between8 and 9 takes place immediately, s t r o n g l y suggesting t h a t a methylidene intermediate i s formed i n Figure 14. 5

3

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10.

GLADYSZ ET AL.


Figure 13. Synthesis of Rh methoxymethyl complex


157

158


Importantly, the f i n a l species under c o n s i d e r a t i o n as an i n termediate i n the CH S0 F induced d i s p r o p o r t i o n a t i o n , methoxymet h y l i d e n e [(n-C H )Re(N0)(PPh )(CH0CH )r S0 F" (10a), i s an i s o l able product of the r e a c t i o n s i n Figures 14 and 157" It i s most e a s i l y obtained when the r e a c t i o n i n Figure 14 i s conducted i n t o l u e n e , under which c o n d i t i o n s 10a p r e c i p i t a t e s as a toluene s o l vate. As w i l l be r a t i o n a l i z e d l a t e r , 10a i s the " t h i r d organometa l l i c product" r e f e r r e d to i n Figure 7 7 " We again attempted t o see i f 10a could be formed by the met h y l a t i o n of formyl 6. We were u n s u c c e s s f u l , and the most e a s i l y i n t e r p r e t e d product d i s t r i b u t i o n s were obtained when 6 was reacted with 0.5 equiv of CH S0 F (Figure 1 6 ) . A g a i n , a c a . T : l mixture of o x i d a t i o n (2b) and reduction ( 9 , accompanied by a small amount 3

5

3

5

3

3

3

3

3

of "over-reduceH" 7) products were obtained.

Methoxymethylidene

10a would represent" a p l a u s i b l e i n i t i a l product which might r a p i d Ty~abstract hydride from s t a r t i n g formyl 6. This hypothesis was tested as shown i n Figure 17. Indeed, when i s o l a t e d 10a and 6 were independently reacted i n a H NMR monitored r e a c t i o n at -70 ° C , 2b and 9 formed c l e a n l y and immediately. Since having authentic samples of 8 , 9 , and 10a enabled us t o r i g o r o u s l y i n t e r p r e t H NMR monitored r e a c t i o n s , we~retumed to the r e a c t i o n of formyl 6 with ChhS0 F under c o n d i t i o n s s i m i l a r to those i n Figure 7. A c c o r d i n g l y , the a d d i t i o n of 1 equiv of C H S0 F to 6 (0.15 M i n CD C1 ) at -70 °C r e s u l t e d i n a slow r e a c t i o n . A f t e r warming to -40 ° C , formyl 6, 2b, 7, 9 , and CH S0 F were present i n a 0 . 5 : 1 . 4 : 0 . 3 : 1 . 0 : 1 . 0 ratio;~remaining 6 disappeared w i t h i n 15 minutes. We conclude that at t h i s s t a g e , the d i s p r o p o r t i o n a t i o n has passed e s s e n t i a l l y through the f i r s t two steps of the mechanism shown i n Figure 18. With f u r t h e r warming, the r e a c t i o n mixture became heterogeneous. However, commencing at -10 °C and proceeding more r a p i d l y upon a d d i t i o n a l warming, 9 d i s p r o p o r t i o n a t e d to 10a and 7, and ( C H ) 0 formed. This transformation corresponds to steps c-e i n Figure 19. Since § d i d not react with dimethyl ether (Figure 1 3 ) , the d i s s o c i a t i o n step (d) (Figure 18) i s l i k e l y r a p i d ; however, oxonium s a l t 11 could conceivably be the species which i s reduced by 9 (or 6) to~7. TKe mixing of 6 and CH S0 F t h e r e f o r e i n i t i a t e s a complex m u l t i s t e p process i n v o l v i n g numerous b i m o l e c u l a r r e a c t i o n s between species of varying c o n c e n t r a t i o n s . The p r e c i s e d i s t r i b u t i o n of products obtained should reasonably be a s e n s i t i v e f u n c t i o n of r e actant r a t i o s and c o n c e n t r a t i o n s , order of reactant a d d i t i o n , and r e a c t i o n temperature and time. Several l i m i t i n g s t o i c h i o m e t r i e s are p o s s i b l e . A l s o , the sporadic appearance of 10a as a f i n a l product r e s u l t s from the p o t e n t i a l a v a i l a b i l i t y of"two hydride donors (6 or 9) f o r the f i n a l step ( e ) . A slowly warmed r e a c t i o n l

l

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2

3

3

3

2

3

3

should favor Kigher y i e l d s of 10a.

The non-observability of 10a

and 8 (S0 F~ s a l t ) during stepsTa and d of the d i s p r o p o r t i o n a t i o n i s e a s i l y understood i n terms of the r e a c t i o n s i n Figures 14-17. 3


10.

@

°CH S^

X

I H C

0 N

9

3

Q

V

CDCK P P h

V

0

10a

•9 spectroscopic ratios

n' +

^Re

+

y

ON

PPh

H

H

-70°v,

,Nph3

ON

3

C

H

2

1

8

< 3>2°

+

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3

ô

S0 F"

7

3

:

1

I

>

CD C1 * 9

:

1

.

M

M

J .

A

2

T

ON

E

,

Nph3

1

+

^Re.

9

C .

X

P P h

Half-methylation experiment #1

'

• N

I ChL

N

3

1.1

/Re.

N

N

0

N

3

Figure 14.

jT

+

P P h

N

OCH

ά

φ

Je* II 3 X H 0CH

»

-60°C, followed by warming

3

159


GLADYSZ ET AL.

ON

CH.

OCH.

X

|| C

H '

3

1:1

7

?

Vh3

+

/Re*

+

N N

OCH

Q

10b

6

Figure 15. Reason for the nonobserv ability ο] the methylidene complex during the half-methylation experiment

$ ^ , /

o , c R

e

\

I

ON Η

N

0

φ

W

CDCl

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5

"3 h

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3

2b 45% isolated

Figure 16.

+

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e

,Re

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N

$

v

0CH

+

v

0N'pPPh 3

3

9 spectroscopic r a t i o :

7 4.7:1

Half-methylation experiment #2


3

160


P h

3

^ Η

-78°C immediate

3

^ C Η 0CH

^Re ON | P P h +

N

CO

N

Ν)

3

9

3

H C 2

%

1

S0 F"

0

v

0CH

W

3

S 3

S0 F"

3

6

^Re ON | PPh

+

3

3

10a

2b

9

Figure 17. Reason for the nonobservability of the methoxymethylidene complex during the half methylation experiment

Re

"

A

+

C H

3

S 0

3

7

0

°

Re

C

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+

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(a)

3

10a

, S0,F" CO R

HC 2

(c)

e

6

ι

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(-20 °C to 0 ° C )

3

(d) fast

Re HC 2

Re {!

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+

3

0(CH ) 3

2

+ N

0(CH ) 3

2

11 Re I Η

^ 0

or a

S 0

3 " F

or

Re ' * 0CH, s

Re C ^0CH

S 0

3 " F

o

Figure 18. Mechanism of CH SO F induced disproportionation of 6 (ancillary ligands omitted for clarity) s

s


10.

GLADYSZ ET AL.


1.0 equ i ν CF~C0 H

RP ON

H'SÏ H

-

I +

9

|>Ph

0

3

CD C1 2

2

*

" °° 7

C

H /warm I(no

Figure 19.

ON

|| PPh N

ÔH

3

3 CF C0 3

2

12

detectable intermediates)

Detection of hydroxycarbene intermediate in CF C0 H proportionation of 6 3

2


induced dis-

162


A v a i l a b l e data i n d i c a t e that CF C0 H and ( C H ) S i C l r e a c t with 6 by pathways q u a l i t a t i v e l y s i m i l a r to the one i n Figure 18· Protonation r e a c t i o n s are g e n e r a l l y much f a s t e r than a l k y l a t i o n r e a c t i o n s . Thus when 6 and CF C0 H are reacted i n C D C l a t -70 °C, a species whose H NMlTproperties i n d i c a t e i t to be [ ( n - C H ) R e (N0)(PPh )(CH0H)] C F C 0 " ( 1 2 , Figure 19) i s generated c l e a n l y and q u a n t i t a t i v e l y . Deprotonation to 6 occurs i n s t a n t l y when 12 i s reacted with L i ( C H ) B H . The =CH0fl l i g a n d (of which 12 is~the f i r s t d e t e c t a b l e complex t h e r e o f ) i s of some h i s t o r i c a l i n t e r e s t , since i t was i n i t i a l l y p o s t u l a t e d as an intermediate i n the FischerTropsch process i n 1951 [ 3 2 ] . Upon warming, 12 d i s p r o p o r t i o n a t e s to the product mixture shown i n Figure 10 without any d e t e c t a b l e i n t e r m e d i a t e s . R e f e r r i n g to a mechanistic scheme f o r the r e a c t i o n of 6 and CF C0 H analogous to the one i n Figure 18, i t can be concluded t h a t step a i s r a p i d r e l a t i v e to step b at -70 ° C . However, step a must be r e v e r s i b l e , and subsequent d i s p r o p o r t i o n a t i o n o c curs r a p i d l y upon warming. The hydroxyalkyl ( n - C H ) R e ( N 0 ) ( P P h ) (CH 0H) i s a l i k e l y intermediate i n t h i s t r a n s f o r m a t i o n ; Casey and Graham have i s o l a t e d the carbonyl s u b s t i t u t e d homolog (n-C H )Re(N0)(C0)(CH 0H) [ 1 9 , 2TJ. 3

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Overview The preceding r e a c t i o n s have c o n v i n c i n g l y demonstrated t h a t the formyl l i g a n d i n (n-C H )Re(N0)(PPh )(CH0) can be e a s i l y converted to a methyl l i g a n d without the a d d i t i o n of an external r e ducing agent. This r e d u c t i o n , which i s accompanied by a s t o i c h i o metric amount of formyl o x i d a t i o n , occurs well below room temperat u r e . With regard to the r e l a t i o n s h i p of these r e a c t i o n s to c a t a l y t i c CO r e d u c t i o n , three p o i n t s should be r a i s e d : (1) Both heterogeneous and homogeneous CO reduction c a t a l y s t recipes often c o n t a i n e l e c t r o p h i l i c components such as s i l i c a supp o r t s , metal o x i d e s , and A1C1 [1,5^,32,34,35^,36]. (2) There i s s u b s t a n t i a l hydride m o b i l i t y a s s o c i a t e d with homogeneous formyl complexes ( p a r t i c u l a r l y those which are a n i o n i c ) [ 1 0 , 1 1 , 1 2 , 1 3 ] . T h e r e f o r e , the generation of small q u a n t i t i e s of c a t a l y s t - b o u n d formyls (a step which based upon homogeneous precedent i s l i k e l y u p h i l l thermodynamically) might be accompanied by a s i m i l a r e l e c t r o p h i l e - i n d u c e d d i s p r o p o r t i o n a t i o n . (3) The r e a c t i o n s of (n-C H )Re(N0)(PPh )(CH0) described were s t o i c h i o m e t r i c i n e l e c t r o p h i l e "E X~." In each c a s e , an "E0-E" and two (metal) X" species were formed. I f an analogous mechanism i s to operate on a bona-fide CO reduction c a t a l y s t , H must be able to convert these end products back to "E X~" and ( m e t a l ) , c o n c u r r e n t l y forming H 0 . Water i s of course a F i s c h e r Tropsch r e a c t i o n product [1,32]. While the r e d u c t i o n of o x i d i z e d metal species b y H i s commonplace, the suggestion t h a t H may regenerate E X~ species i s more c o n j e c t u r a l . A l s o , as a l l u d e d to e a r l i e r , there i s good evidence t h a t several CO methanation c a t a l y s t s e f f e c t i n i t i a l CO d i s s o c i a t i o n to carbide [1,1]; hence we by 5

5

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+

+

2

+

0

2

2

2

+


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GLADYSZ

E T

AL.


163

no means wish to suggest that electrophilic species may play a role in aVI CO reduction catalysts. In important recent work, Shriver has demonstrated that electrophiles can promote the migration of alkyl groups to coordinated CO. Lewis acid adducts of metal acyl complexes are isolated [37]. Thus it is possible that electrophilic species might also f a c i l i tate the generation of catalyst-bound formyls. In conclusion, the use of homogeneous model compounds has enabled the discovery and elucidation of a new formyl reduction mechanism which merits serious consideration as a reaction pathway on certain CO reduction catalysts. Additional studies of the compounds described in this account are actively being pursued. Acknowledgement We thank the Department of Energy for support of this research. We are also grateful for Fellowship support from the Alfred P. Sloan Foundation (JAG) and the Regents of the University of California (WAK, WT).

References 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17.

Masters, C. Adv. Organomet. Chem., 1979, 21, 61, and references therein. Muetterties, E.L.; Stein, J. Chem. Rev., 1979, 79, 479, and references therein. Olivé, G.H.-; Olivé, S. Angew. Chem., Int. Ed. Engl., 1979, 18, 77. Pruett, R.L. Ann. N.Y. Acad. Sci., 1977, 295, 239. Fraenkel, D.; Gates, B.C. J . Am. Chem. Soc., 1980, 102, 2478. Clark, G.R.; Headford, C.E.L.; Marsden, K.; Roper, W.R.J.Am. Chem. Soc., 1979, 101, 503. Wong, K.S.; Labinger, J.A. J . Am. Chem. Soc., 1980, 102, 3652. Wong, Α.; Harris, M.; Atwood, J.D. J. Am. Chem. Soc., 1980, 102, 4529. Wolczanski, P.T.; Bercaw, J.E. Accts. Chem. Res., 1980, 13, 121. Gladysz, J.Α.; Williams, G.M.; Tam, W.; Johnson, D.L. J. Organomet. Chem., 1977, 140, Cl. Gladysz, J.Α.; Selover, J.C. Tetrahedron Lett., 1978, 319. Gladysz, J.A.; Tam, W. J . Am. Chem. Soc., 1978, 100, 2545. Gladysz, J.A.; Merrifield, J.H. Inorganica Chimica Acta, 1978, 30, L317. Gladysz, J.Α.; Selover, J.C.; Strouse, C.E. J. Am. Chem. Soc., 1978, 100, 6766. Tam, W.; Wong, W.-K.; Gladysz, J.A. J . Am. Chem. Soc., 1979, 101, 1589. Wong, W.-K.; Tam, W.; Strouse, C.E.; Gladysz, J.A. J. Chem. Soc., Chem. Commun., 1979, 530. Wong, W.-K.; Tam, W.; Gladysz, J.A. J . Am. Chem. Soc., 1979, 101, 5440.


164


18. Kiel, W.A.; Lin, G.-Y.; Gladysz, J.A. J. Am. Chem. Soc., 1980, 102, 3299. 19. Casey, C.P.; Andrews, M.A.; McAlister, D.R.; Rinz, J.E. J. Am. Chem. Soc., 1980, 102, 1927. 20. Stewart, R.P.; Okamoto, N.; Graham, W.A.G. J. Organomet. Chem. 1972, 42, C32. 21. Sweet, J.R.; Graham, W.A.G. J. Organomet Chem., 1979, 173, C9. 22. Fischer, E.O.; Strametz, H. Z. Naturforsch. Β., 1968, 23, 278. 23. Shvo, Y.; Hazum, E. J. Chem. Soc., Chem. Commun., 1975, 829. 24. Blumer, D.J.; Barnett, K.W.; Brown, T.L. J. Organomet. Chem., 1979, 173, 71. 25. Collman, J.P.; Finke, R.G.; Cawse, J.N.; Brauman, J.I. J. Am. Chem. Soc., 1978, 100, 4766. 26. Casey, C.P.; Bunnell, C.A. J. Am. Chem. Soc., 1976, 98, 436. 27. W.A. Kiel and A.T. Patton, unpublished results, UCLA, 1980. 28. Brookhart, M.; Nelson, G.O. J. Am. Chem. Soc., 1977, 99, 6099. 29. Schrock, R.R.; Sharp, P.R. J. Am. Chem. Soc., 1978, 100, 2389. 30. Brookhart, M.; Tucker, J.R.; Flood, T.C.; Jensen, J. J. Am. Chem. Soc., 1980, 102, 1203. 31. Schwartz, J.; Gell, K.I. J. Organomet. Chem., 1980, 184, Cl. 32. Storch, H.H.; Columbic, N.; Anderson, R.B. "The Fischer-Tropsch and Related Syntheses," Wiley, New York, 1951. 33. Demitras, G.C.; Muetterties, E.L. J. Am. Chem. Soc., 1977, 99, 2796. 34. Doesburg, E.B.M.; Orr, S.; Ross, J.H.R.; van Reijen, L.L. J. Chem. Soc., Chem. Commun., 1977, 734. 35. Nijs, H.H.; Jacobs, P.A.; Uytterhoeven, J.B. J. Chem. Soc., Chem. Commun., 1979, 1095. 36. Ichikawa, M. J. Chem. Soc., Chem. Commun., 1978, 566. 37. Butts, S.B.; Strausse, S.H.; Holt, E.M.; Stimson, R.E.; Alcock, N.W.; Shriver, D.F. J. Am. Chem. Soc., 1980, 102, 5093. RECEIVED December

8, 1980.


Electrophile-Induced Disproportionation of the Neutral Formyl (Î·

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