J . Am. Chem. SOC. 1984, 106, 2913-2917
2913
Neighboring Group Participation of Halo and Aryl Groups in the Stoichiometric and Catalytic Reactions of Olefins with Transition-Metal Hydrides and a New Route to Arene Complexes Robert H. Crabtree,* Michelle F. Mellea, and Jennifer M. Quirk Contribution from Yale University Chemistry Department, Sterling Chemistry Laboratory, New Haven, Connecticut 0651 1. Received October 19, 1983
Abstract: [IrH,(MezC0)2(PPh3)21BF,(1) reacts with ArCH=CH2 to give [Ir(06-ArEt)L2]BF4(2, Ar = Ph, 2,6-MezC6H3, p-MeOC6H4,PhCH2, Ph(CH,),, 2,6-C1&6H3, and 2-XC6H4(X = C1, or Br]). For the first three substrates, a neighboring group participation of the aryl group via an ?,-benzyl intermediate is proposed. For the next two, isomerization takes place to give a styrene derivative which then reacts as above. For the halogen-containing substrates the unusual intermediates [ IrH2(a3-XC6H4CH=CH2)L2]BF,are observed, in which the substrate chelates to the metal via the (C=C) and halo groups. These are rare examples of both a halocarbon complex and an olefin dihydrido complex. The high branched:linear isomer ratios generally observed in the hydroformylation and hydrosilation of styrene are interpreted in terms of neighboring group participation via an s3-benzyl intermediate. Halo and aryl groups are suggested as candidtates for study in connection with directing effects and asymmetric induction in homogeneous catalysis.
One of the most persuasive cases for the use and study of homogeneous rather than heterogeneous catalysts is the superior selectivity often shown by homogeneous systems. This is an important property in a variety of applications because it makes expensive or tedious purification steps unnecessary and avoids the loss of product inherent in an unselective process. The question that arises is whether the factors leading to high selectivity can be understood, to help in what might otherwise be an empirical search for selective homogeneous catalysts. The purpose of this paper is to emphasize the importance of a neighboring group participation in determining selectivity and to describe this effect for halo and aryl groups, which up to now might now have been considered unpromising candidates. We shall first describe the chemistry and then discuss its implications.
Results During attempts to dehydrogenate alkanes with [ IrH2S2L2]BF,' (1, S = Me2CO; L = PPh,) we screened a large number of olefins as hydrogen acceptors for the reaction (eq 1). The most successful
3h +
2s (1)
L=PPh,;S=Me,CO
hydrogen acceptor was tert-butylethylene, but a number of apparently equally suitable alkenes failed, e.g., styrene. In order to find out why this was so, we looked a t the reaction of various vinylarenes with 1 and found the unexpected reaction2 shown in eq. 2, which constitutes a novel route to arene complexes. The
2
new complexes 2 were ineffective in alkane dehydrogenation under (1) Crabtree, R. H.; Mihelcic, J. M; Quirk, J. M. J . Am. Chem. SOC.1979, 101, 7138; 1982, 104, 107. (2) Crabtree, R. H.; Mellea, M. F.; Quirk, J. M. J . Chem. SOC.,Chem. Commun. 1981, 1217
0002-7863/84/ 1506-2913$01.50/0
the conditions of eq 1, accounting for the failure of vinylarenes as hydrogen acceptors. The reactions of eq 2 generally went in CH2C12a t room temperature over 30 s in 80-97% yield. They were accompanied by a color change from colorless to orange. The addition of E t 2 0 at this stage led to the isolation of the new complexes. These air-stable microcrystalline orange fluoroborate salts were readily recrystallized from CH2C12/Et20. The identity of the products followed from the spectroscopic data in Table I. Taking the example of [Ir(q6-PhEt)L2]BF4(2), the I R spectrum (CDC1, solution) showed aliphatic C-H vibrations at 2927 cm-' and the B-F vibrations at 1061 cm-I. The 'H N M R spectrum showed strong coordination shifts of the $-ring protons but only minor shifts in the ethyl side chain., The resonance positions (6) of the PhEt group together with the coordination shifts (ppm) (in parentheses) from free PhEt were as follows: 1.3 (+0.005) Me; 2.6 (-0.08) CH,; 5.0 (2.2) o-CH; 5.4 (1.8) m-CH; 6.9 (-0.3) p-CH. The identity of each resonance was confirmed by decoupling experiments. The low coordination shifts we observe for the ethyl side chain suggest this group is not interacting with the metal. The other @-arene complexes gave similar spectra. Mechanism. In order to check that the hydrogen incorporated in the styrene really does come from 1, we studied the reaction using [IrD2S2L2]BF,(8-1). The product was entirely d2-2 as confirmed by 2H N M R and IR. In particular, the 2H N M R of 8 - 2 showed two peaks of equal intensity a t 6 1.2 and 2.5 as expected. An external arene did not interfere with the reaction; for example, no $-styrene complex was ever seen even though reaction 2 was run in a large excess of styrene, nor was any q6-toluene complex seen in the presence of a large excess of toluene in the solvent medium. Finally, no v6-ethylbenzene complex was formed from 1, tert-butylethylene, and ethylbenzene under similar conditions. The aryl and vinyl groups must be present in the same molecule for the reaction to occur, therefore this is an authentic example of neighboring group p a r t i ~ i p a t i o n . ~ Other Vinylarenes. We were interested to know how far the side chain could be extended and still give the q6-arene product. Allylbenzene, PhCH2CH=CH2, reacts under the same conditions as styrene to give the analogous a6-propylbenzene product. At first sight, therefore, the reactions might seem to go via PhCH2CH(CH3)[Ir] (where [Ir] represents the metal and asso( 3 ) Haines, L. M. Inorg. Chem. 1971, 10, 1685. (4) Page, M. I. Chem. SOC.Rev. 1973, 2, 295.
0 1984 American Chemical Society
2914 J . Am. Chem. Soc., Vol. 106, No. 10, 1984
Crabtree, Mellea. and Quirk
Table I. Spectral, Analytical, and Yield Data for the New Complexes _ __________~_ _____-
productb
arenea
time,' complexes temp ('C)
PhCH=CH,
2
30 s
97
PhC H ,CH =CH ,
2
30 s
93
Ph(CH,),CH=CH, or PliCH,CH=CHCH, trans-PhCH=CHPh o r cis-PhCH=CHPh 2,6-Mc,C6 H,CH=CH,
2
30 s
91
2 2
30 s 2h 30 s
88 85 94
PhC (Me)=CH
2
30 s
93
p-MeOC, H,CH=CH,
2
5 min
80
2,6-C1,C6 H,CH=CH,
5
15 min
83
2,6-C1,C6 H,CH=CH, 2-C1C6 H,CH=CH,
2 5
1 h,40 20 min, -13
80 (quant.)
2-C1C, H,CH=CH,
2
20 min
95
2-RrC6 H,CH=CH,
5
20 niin, 7
(quant.)
2- BrC, H, C H=CH,
2
2-1C, H,CH=CH,
5
PhCH=CH,'
6
2h 20 niin, 10
5 min
ana1ysis.f v _____
yield? h '
90 (qu an t .)
(quan t .)
C
' H NMR' 1.3, t ( 8 ) , M e ; 2 . 6 , q ( 8 ) , C H 2 ; 5 . 0 ,d ( 6 ) , o - H : 5 . 4 , dd ( 6 , 81, m-H; 6.9, dd ( 6 , 8) p-Hh 0.9,t(7),Me:1.5,~,P-CH,;2.5,t (8),@-CH2:5.0,d (6.5), o-H; 5.5, dd (5.3,6.6), m-Hi6.9, t ( 5 . 3 1 , ~ - H 1.09, t (8),Me; 1.35, c, p- and r-CH,; 2.45, c, a-CH,: 4.94, d (5.4), o-H; 5.41, t ( 7 ) , m-H
58.57 (58.72) 56.54 (56.63) 56.10 (56.06)
H
of cryd
4.56 (4.45) 4.61 0.5 (4.46) 4.78 0.75 (4.55)
2.67,c,CH2;4.85,d(6.8),o-H;5.39,dd(6,8),m-H; i 6.96, t (6.8),p-H 1.03, t (8.1). Me; 2.55, q (8.1), CH,; 2.17, S , 0-Me; 5.17, d (7.5),m-H: 5.45, t (7.5), p-H 1.49, c , Me; 2.84, c, CY-CH;5.08 and 5.37, c, 0- and m-H 1.09, t (8), Me;2.49, q (8), CH,: 3.78, s, M e 0 ; 4 . 5 3 , d (6.5), m-H; 5.4, d (6.6),0-Hh -26.3, dt (7.2,l 14.4m), IrHF;" -8.5, dt (7.2,' 16.9m), IrHG; 3.09, dt (6.4,m I O p ) , H A ; 3.68, d (lo'), HB; 5.45, ddd ( l o ? 1O,q, IOm), I I c ; 6 . 7 5 , d ( 8 ) , HD; 7.09, t ( 8 ) , HE 1.09, t ( 7 ) , Me; 2.80, q (7), CH,; 5.21, c, m-H; 5.6, c, p-H -26.7, dt (6.6,' 13.2,m), h H F ; " -8.7, dt (6.6,' 1 9 m ) , IrHG; 3.13, C , HA: 3.67, d (9.9),' HB; 5.21, ddd (IO? 10,Q l o m ) , H c : 6 . 7 , d ( 8 . 2 4 ) , a n d 6 . 9 , c, H ~ , a n dH y ; 7.03, c, HD or HE 1.25, t (8.3), Me; 2.77, q (8.3), C H 2 ; 4 . 3 9 , d (S), and 4.5, d (6.6) IID', and Hy;" 6.8, c, HD -25, dt (6.6,'13.2"), IrHF;" -8.85 d t (6.6,' 18.1m), I r H G ; 3 , C, H ~ ; 3 . 7 , d d(3.3; 9'1, H ~ i 5 . 1 5ddd , ( 1 1,P l l , q 1 l m ) , H,;6.8, d 16.6), kind 6.9, c , HD'. - and H y ; 7.06, c, HD o r f i ~ 1.24, t (6.6), Mc; 2.78, q (6.6), CH,;4.4, d (6.6), a n d 4.5, d (6.6), HD', and Hy;" 6.8, c, HD -21.3, dt (6.6,' 13.2m), h H F i n -9.14, dt (6.6,' 18.1m),lrHG;2.9,dd(5,s 1 1 . 5 P ) , H ~ ; 3 . 7 , C , H ~ ; 5.12, c, HC; 6.7, d (6.6), and 7.0, c, HD and H y ; 7.15, c, HD or HE 1 , t (10.3), Me;2.3, q ( 1 0 . 3 ) , C H 2 ; 5 . 1 , c t f(8.2),0-H; 5.52, c, m-H;' 6.78, c , p-H'
57.49 (57.61) 56.99 (57.20) 53.86 (54.49)
4.62 (4.62) 4.52 (4.48) 4.51 (4.34)
0.33 0.33
1.0
i
j
i
i i
Type of complex formed. The colors of the complexes were as follows: 2, orange;S, colorless: 6, yellowa Used in the reaction with 1 . orange. ' Conditions of the formation reaction (at 15 "C unless stated). When the temperature shown was below 1 5 "C, this was also the Of purified product, or, when the yield is shown in parentheses, the yield in solution estitemperature at which the H NMR was recorded. mated by integration of the appropriate ' H NMR spectrum. '' In CDCI, at 20 "C (but see footnote c). Reported as-position i s ) , multipliCalculated values in parentheses. i( Mol of CH,Cl, per iridium a t o m , by microanalysis and concity (coupling constant (Hz)), assignment. firnicdby ' H NMR. I3CNMR: 15,Me;27,CH2;93.6and95.4,p-andm-C;98.5,ipso-C;120.7,o-C;128, 1 2 8 , 1 3 0 . 5 , a n d 134.1,PPh3. ' PhCH=CHCH, gave comparable results. Not analyzed. In 6 and cases involving haloarenes, the products were not very stable. Spec,J(H,P), confirmed by 31P dccoupling in the case of 2,6-dichlorostyrene. " See I:igure 1 for assigntrum recorded at -60 "C. 'J(H,H). Reaction with IRhH,(I:tOH),(PPh,),]PI h . ' Additional couplings At 4 0 "C. s 'J(HA,Hg). ment key. ' J ( H ~ , b i g ) . 'J(H*,Hc!. identified as 'J(Rh,H) by comparison with the analogous iridium comples.
'
'
ciated ligands). A variable-temperature 'H N M R study showed that this was not in fact so. 'H N M R studies from 160 to 300 K in an N M R tube show that the reaction proceeds via free propenylbenzene, PhCH=CHCH3. On warming a mixture of allylbenzene (10 molar equiv) and 1, the first sign of reaction is seen a t 183 K. The hydride resonances of 1 disappear and are replaced by new peaks, including a triplet a t -13.6 6 which may well arise from [IrH2(PhCH2CH=CH2)2L2]f,since the corresponding styrene complex2 has almost identical resonances. At 240 K, peaks due to free propenylbenzene appear in the spectrum, and by the time 245 K is reached the whole of the allylbenzene present has been catalytically converted to free propenylbenzene. Only at 290 K do the characteristic peaks of the product [(q6PhPr)IrL,]+ begin to appear. The same product is formed directly when propenylbenzene reacts with 1. Ph(CH2)2CH=CH2 also reacts with 1 to give an analogous complex. Detailed study showed that, as in the case of allylbenzene, isomerization preceded the formation of 2. This was first observed a t 215 K and at 265 K only P-ethyl styrene was present. Complex 2 was formed above 290 K. We decided to examine allyl phenyl ether, because in this compound the vinyl group cannot move into conjugation with the ring. At -60 OC the isomerization of the compound to propenyl phenyl ether is so fast that it is complete before the first N M R
'
Scheme I. The Reactions of [IrH,S,L,] BI', ( 1 ) with Vinylarenes"
3
4 [ I r ] refers t o the metal and associated ligands.
spectral data can be collected a t 215 K. Related isomerizations a t higher temperatures have been r e p ~ r t e d . ~At room temperature, the acetone complex 1 hydrogenated allyl propenyl ether to give uncharacterizable iridium-containing materials; no trace ( 5 ) Baudry, D.; Ephritkine, M.; Felkin, H. N o w . J . Chim.1978, 2, 355.
J. Am. Chem. SOC.,Vol. 106, No. IO, 1984 291 5
Reactions of Styrenes
*
