Addition of OH and alcohols or amines to -C≡N and -CH=CH2 groups of CH2=CHCN coordinated to Cp*Ir(η3-CH2CHCHPh)

Article abstract of DOI:10.1021/om0002881

Hydroxide ion and alcohols or amines are added regioselectively to the -C≡N and -CH= CH₂ groups of CH₂=CHCN in [Cp*Ir(η³-CH₂CHCHPh)(NCCH=CH₂)] ⁺ (1a). The unsaturated amido complex Cp*Ir(η³-CH₂CHCHPh)(NHCOCH=CH₂) (2a), alkoxo amido complexes Cp*Ir-(η³-CH₂CHCHPh)(NHCOCH₂CH ₂OR) (4, R = Me (a), Et (b)), amino amido complexes Cp*Ir-(η³-CH₂CHCHPh)(NHCOCH₂CH ₂NR₂) (6, R₂ = Me₂ (a), (Me)(H) (b)), and an amino iminoether complex [Cp*Ir(η³-CH₂CHCHPh)(NH=C(OMe)CH ₂CH₂NMe₂)]⁺ (8) have been prepared from the reactions of 1a with OH^-, OR^-/ROH (R = Me, Et), OH-/HNR₂ (R₂ = Me₂, (Me)-(H)), and MeOH/NHMe₂, respectively. Reactions of 2, 4, 6, and 8 with aqueous HCl yield Cp*IrCl(η³-CH₂CHCHPh) and quantitative amounts of H₂NCOCH=CH₂ H₂NCOCH₂CH₂-OR, H₂NCOCH₂CH₂NR₂, and MeOCOCH₂CH₂NMe₂, respectively. Crystal structures of 1a and 4a have been determined by X-ray diffraction data analysis.

Full text of DOI:10.1021/om0002881

Organometallics 2000, 19, 4043-4050
4043
Ad d ition of OH- a n d Alcoh ols or Am in es to -CtN a n d
-CHdCH2 Gr ou p s of CH2dCHCN Coor d in a ted to
Cp *Ir (η3-CH2CHCHP h )
Chong Shik Chin*,† Daesung Chong,† Soojin Lee,† and Young J a Park‡
Department of Chemistry, Sogang University, Seoul 121-742, Korea, and Department of
Chemistry, Sookmyung Women’s University, Seoul 140-742, Korea
Received April 5, 2000
Hydroxide ion and alcohols or amines are added regioselectively to the -CtN and -CHd
CH2 groups of CH2dCHCN in [Cp*Ir(η3-CH2CHCHPh)(NCCHdCH2)]+ (1a ). The unsaturated
amido complex Cp*Ir(η3-CH2CHCHPh)(NHCOCHdCH2) (2a ), alkoxo amido complexes Cp*Ir-
(η3-CH2CHCHPh)(NHCOCH2CH2OR) (4, R ) Me (a ), Et (b)), amino amido complexes Cp*Ir-
(η3-CH2CHCHPh)(NHCOCH2CH2NR2) (6, R2 ) Me2 (a ), (Me)(H) (b)), and an amino imino-
ether complex [Cp*Ir(η3-CH2CHCHPh)(NHdC(OMe)CH2CH2NMe2)]+ (8) have been prepared
from the reactions of 1a with OH-, OH-/ROH (R ) Me, Et), OH-/HNR2 (R2 ) Me2, (Me)-
(H)), and MeOH/NHMe2, respectively. Reactions of 2, 4, 6, and 8 with aqueous HCl yield
Cp*IrCl(η3-CH2CHCHPh) and quantitative amounts of H2NCOCHdCH2, H2NCOCH2CH2-
OR, H2NCOCH2CH2NR2, and MeOCOCH2CH2NMe2, respectively. Crystal structures of 1a
and 4a have been determined by X-ray diffraction data analysis.
In tr od u ction
tion of OH-, ROH, and HNR2 to both the nitrile (Nt
C-) and olefinic (-CHdCH2) groups of CH2dCHCN
coordinated to iridium. To the best of our knowledge,
there has been no report made on the addition of
nucleophiles to both the nitrile and olefinic groups of
unsaturated nitriles coordinated to metals.
Nitriles coordinated to transition metals show reac-
tivity toward nucleophiles different from that of free
nitriles probably because the coordination through the
nitrogen atom increases the nucleophilicity of the carbon
of the nitrile (NtC-R).1 Reactions of nitriles such as
hydrolysis2,3 and alcoholysis3 are known to be catalyzed
by metal complexes. Hydrolysis of unsaturated nitriles
such as H2CdCHCN produces unsaturated amides,
which are polymerized to produce chemicals that are
used in paper industry and wastewater treatment.4 We
recently reported the addition of OH-, alcohols, and
amines to CH3CN coordinated to iridium to produce
amido (Ir-NHCOCH3), imino-ether (Ir-NHdC(OR)-
CH3), and amidine complexes (Ir-NHdC(NR2)CH3) and
catalytic production of amides by these iridium com-
plexes.3 We now wish to report the simultaneous addi-
Resu lts a n d Discu ssion
Iridium complexes of unsaturated nitriles, [Cp*Ir(η3-
CH2CHCHPh)(NCCRdCH2)]+ (1, R ) H (a ), CH3 (b))
and [Cp*Ir(η3-CH2CHCHPh)(NCCH2CH2OCH3)]+ (1c)
have been prepared by the known method for complexes
of saturated nitriles (see Experimental Section).3,5
P r op er ties of CH2dCHCN in [Cp *Ir (η3-CH2CH-
CHP h )(NCCHdCH2)]+ (1a ). The crystal structure of
1a (Figure 1) reveals somewhat interesting results that
the bond distance of CtN (1.141(14) Å) of CH2dCHCN
is decreased upon coordination to Cp*Ir(η3-CH2CHCHPh)
from that (1.163(1) Å) of free CH2dCHCN, while the
CdC distance (1.353(2) Å) is increased from that
(1.339(1) Å) of free CH2dCHCN. These results are
different from the data previously reported for Ni-NC-
CHdCH2 and Cu-NC-CHdCH2, where the CdC dis-
tances are shorter than that of free CH2dCHCN.1c This
lengthening of the CdC distance of CH2dCHCN in 1a
led us to expect an increase in reactivity of the CdC
group.
† Sogang University.
‡ Sookmyung Women’s University.
(1) (a) Michelin, R. A.; Mozzon, M.; Bertani, R. Coord. Chem. Rev.
1996, 147, 299. (b) Endres, H. In Comprehensive Coordination Chem-
istry; Willkinson, G., Gillard, R. D., McCleverty, J . A., Eds.; Perga-
mon: Oxford, 1987; Vol. 2, p 261. (c) Bryan, S. J .; Huggett, P. G.; Wade,
K.; Danials, J . A.; J ennings, J . R. Coord. Chem. Rev. 1982, 44, 149.
(2) (a) J ensen, C. M.; Trogler, W. C. J . Am. Chem. Soc. 1986, 108,
723. (b) Arnold, D. P.; Bennett, M. A. J . Organomet. Chem. 1980, 199,
119. (c) Yoshida, T.; Matsuda, T.; Okano, T.; Kitani, T.; Otsuka, S. J .
Am. Chem. Soc. 1979, 101, 2027. (d) Bennett, M. A.; Yoshida, T. J .
Am. Chem. Soc. 1978, 100, 1750. (e) Bennett, M. A.; Yoshida, T. J .
Am. Chem. Soc. 1973, 95, 3030. (f) McKenzie, C. J .; Robson, R. J . Chem.
Soc., Chem. Commun. 1988, 112. (g) Gaset, G. V. A.; Kalck, Ph. J .
Mol. Catal. 1981, 12, 103. (h) Villain, G.; Kalck, Ph.; Gaset, A.
Tetrahedron Lett. 1980, 2901. (i) Kaminskaia, N. V.; Kostic, N. M. J .
Chem. Soc., Dalton Trans. 1996, 3677. (j) Murahashi, S.-I.; Naota, T.;
Saito, E. J . Am. Chem. Soc. 1986, 108, 7846. (k) Dixon, N. E.; Fairlie,
D. P.; J ackson, W. G.; Sargeson, A. M. Inorg. Chem. 1983, 22, 4038.
(l) Kabalka, G. W.; Deshpande, S. M.; Wadgaonka, P. P.; Chatla, N.
Synth. Commun. 1990, 1445.
Rea ction of [Cp *Ir (η3-CH2CHCHP h )(NCCRd
CH2)]+ (1) w ith OH-. Unsaturated nitriles, CH2d
CRCtN (R ) H (a ), CH3 (b)), in [Ln-Ir-NtCCRd
CH2]+ (1, Ln ) Cp*(η3-CH2CHCHPh)) react with OH-
to give amido complexes 2, leaving the olefinic group
intact (eq 1). Comparing the detailed spectral (1H and
13C NMR, IR) data for 2 with extensive data for related
(3) Chin, C. S.; Chong, D.; Lee, B.; J eong, H.; Won, G.; Do, Y.; Park,
Y. J . Organometallics 2000, 19, 638.
(4) (a) Matsuda, F. CHEMTECH 1977, 306. (b) Casey, J . M. Pulp
and Paper, 3rd ed.; Wiley-Intercience: New York, 1981; Vol. 2, p 1269,
Vol. 3, p 1449.
(5) J eong, H.; J oo, K.-S.; Chin, C. S. Bull. Korean Chem. Soc. 1997,
18, 402.
10.1021/om0002881 CCC: $19.00 © 2000 American Chemical Society
Publication on Web 08/26/2000

4044 Organometallics, Vol. 19, No. 20, 2000
Chin et al.
production of the unsaturated amides H2NCOCRdCH2
1
(3, identified by H NMR and mass spectra) from the
reactions of 2 with HCl (eq 1).
R ea ct ion s of [Cp *Ir (η3-CH 2CH CH P h )(NCCHd
CH2)]+ (1a ) w ith Alcoh ols in th e P r esen ce of OH-.
Reactions of 1a with alcohols (ROH) in the presence of
OH- readily give the alkoxo amido complexes Ln-Ir-
NHCOCH2CH2OR (4) (eq 2), which have been unam-
biguously characterized by detailed spectral and el-
emental analysis data (see below) and also by crystal
structure determination for 4a by X-ray diffraction data
analysis.
F igu r e 1. ORTEP drawing of [Cp*Ir(η3-CHPhCHCH2)(Nt
CCHdCH2)]OTf (1a ) with 30% thermal ellipsoids prob-
ability. Selected bond distances (Å): Ir1-N ) 2.038(10);
Ir1-C14 ) 2.182(11); Ir1-C15 ) 2.148(11); Ir1-C16 ) 2.223-
(12); C14-C15 ) 1.401(17); C15-C16 ) 1.463(16); N-C13
)
1.141(14); C13-C12 ) 1.40(2); C12-C11 ) 1.353(2). Selected
bond angles (deg): Ir1NC13 ) 176.6(11); NC13C12 ) 175.8-
(16); C13C12C11 ) 138(3). Counteranion (OTf) and hydrogen
atoms are omitted for clarity.
amido complexes2a,b,e,3,6 unambiguously characterizes
the unsaturated amido-iridium complexes 2 as shown
in eq 1.
It is noticed that distances of C(21)-C(22) (1.45(2) Å)
and C(20)-N (1.309(16) Å) in 4a are somewhat shorter
than the average values of C(sp3)-C(sp3) (1.53 Å) and
C(sp2)-N (1.38 Å),7 respectively, while those of C(20)-
O(1) (1.236(16) Å) and C(20)-C(21) (1.491(18) Å) are
close to the average values of C(sp2)dO (1.21 Å) and
C(sp2)-C(sp3) (1.51 Å),7 respectively (Figure 2).
The reaction of 1b with CH3OH is so slow that most
of 1b was recovered after 18 h of the reaction at room
temperature. 1H NMR measurements show several
weak and broad signals, which are not fully assigned.
Under the refluxing conditions in CHCl3, however, the
reaction of 1b with CH3OH gives unidentified compound-
(s).
1
The H NMR spectrum of 4a in C6D6 clearly shows
all the signals due to η3-CHHCHCHPh and -COCH2C-
HHOCH3. Deuterium labeling experiments also confirm
the assignments of the signals due to the methylene
protons, Ir-NHCOCH2CHHOCH3. The triplet at δ 2.56
1
The H NMR spectra of 2 in C6D6 clearly show the
1
for 4a completely disappears in the H NMR spectrum
signals due to every proton of CHHCHCHPh and NH-
CO-CRdCHH (R ) H, CH3). The signals at δ 170.7 (2a )
and 174.6 (2b) in the 13C NMR spectra and strong IR
absorptions at 1595 (2a ) and 1588 cm-1 (2b) also
suggest the carbonyl moiety, Ir-NH-CO-CRdCH2, in
2 as observed previously for Ln-Ir(-NH-CO-CH3),
whose crystal structure was also determined by X-ray
diffraction data analysis.3 There seems to be an isomer-
ization between two isomers Ln-Ir(-NH-COCHdCH2)
(2a ) and Ln-Ir(-NdC(OH)CHdCH2) (2a E) in chloro-
(see Supporting Information) of the Ir complex obtained
from the reaction of 1a with NaOD and CH3OD. This
observation suggests that the triplet at δ 2.56 is due to
Ln-Ir-NHCOCH2CH2OCH3 of 4a , and the d 2 isoto-
pomer Ln-Ir-NHCOCD2CH2OCH3 (4a -d 2)8 is obtained
from the reaction of 1a with NaOD and CH3OD (see
below).
(6) (a) Suh, M. P.; Oh, K. Y.; Lee, J . W.; Bae, Y. Y. J . Am. Chem.
Soc. 1996, 118, 777. (b) Cini, R.; Fanizzi, F. P.; Intini, F. P.; Maresca,
L.; Natile, G. J . Am. Chem. Soc. 1993, 115, 5131. (c) Woon, T. C.;
Fairlie, D. P. Inorg. Chem. 1992, 31, 4069. (d) Fairlie, D. P.; Woon, T.
C.; Wickramasinghe, W. A.; Willis, A. C. Inorg. Chem. 1994, 33, 6425.
(e) Curtis, N. J .; Sargeson, A. M. J . Am. Chem. Soc. 1984, 106, 625. (f)
Creaser, I. I.; Harrowfield, F. G.; Sargeson, A. M. J . Am. Chem. Soc.
1981, 103, 3559. (g) Dixon, N. E.; Fairlie, D. P.; J ackson, W. G.;
Sargeson, A. M. Inorg. Chem. 1983, 22, 4083.
(7) March, J . Advanced Organic Chemistry, 4th ed.; Wiley-Inter-
science: New York, 1992; p 21.
(8) Nondeutrated H2O was used in the isolation of 4a -d 2 (see
Experimental Section for detailed procedure), which may explain how
the isolated 4a -d 2 has the hydrogen (rather than deuterium) bound to
the nitrogen in L-Ir-NHCOCD2CH2OCH3 (4a -d 2).
form since two sets of all the H and 13C NMR signals
1
are measured in CDCl3 (see Supporting Information for
the spectra of H and 13C NMR in CDCl3) as observed
1
for Ln-Ir(-NHCOCH3) (keto form in 100% in C6D6) and
Ir(-NdC(OH)CH3) (enol form as the minor product in
CDCl3).3 It may be also mentioned that exactly the same
1H and 13C NMR spectra in C6D6 are regenerated when
CDCl3 is removed from the solution of 2a and 2a E in
CDCl3 and the resulting solid is redissolved in C6D6. The
unsaturated amido moiety in 2 is also supported by

CH2dCHCN Coordinated to Cp*Ir(η3-CH2CHCHPh)
Organometallics, Vol. 19, No. 20, 2000 4045
F igu r e 2. ORTEP drawing of Cp*Ir(η3-CH2CHCHPh)-
(NHC(dO)CH2CH2OMe) (4a ) with 30% thermal ellipsoids
probability. Selected bond distances (Å): Ir1-N ) 2.073-
(11); Ir1-C11 ) 2.144(6); Ir1-C12 ) 2.110(11); Ir1-C13
)
2.221(12); C11-C12 ) 1.429(18); C12-C13 ) 1.418(18); N-C20
) 1.309(16); O1-C20 ) 1.236(16); O2-C22 ) 1.391(18); O2-
C23 ) 1.407(19); C20-C21 ) 1.491(18); C21-C22 ) 1.45(2).
Selected bond angles (deg): Ir1NC20 ) 132.9(10); NC20C21
) 119.9(15); NC20O1 ) 121.4(13); O1C20C21 ) 118.7(14);
C
20C21C22 ) 113.6(13); C21C22O2 ) 112.7(14); C22O2C23
)
110.8(14).
The assignments above are also unambiguously sup-
1
1
1
ported by H, H-2D COSY, and H, 13C-2D HETCOR
spectra for 4a (see Supporting Information). Methoxo
amide H2NCOCH2CH2OCH3 (5a ) is quantitatively ob-
tained from the reaction of 4a with aqueous HCl (eq 2).
1
The H NMR spectrum of 4a in CDCl3 (Figure 3b and
F igu r e 3. 1H NMR spectra of Cp*Ir(η3-CH2CHCHPh)-
(NHC(dO)CH2CH2OMe) (4a ) and Cp*Ir(η3-CH2CHCHPh)-
(NdC(OH)CH2CH2OMe) (4a E) in different deutrated sol-
vents, (a) C6D6, (b) CDCl3, (c) CD3COCD3 (25 °C), and (d)
CD3COCD3 (-30 °C) at 500 MHz.
Supporting Information) shows a set of small signals
(less than 15% of the corresponding signals of the major
compound, 4a ) which are assigned to those of the enol
form isomer Ln-Ir-NdC(OH)CH2CH2OCH3 (4a E) as
discussed above for 2a in C6D6 and 2a E (in small
amount) in CDCl3.
tion of the R-carbon of CH2dCHCN is facilitated by
coordination to a metal.1c
1
It is noticed that the H NMR spectrum of 4a in C6D6
shows one signal for the two protons of the keto form,
Ln-Ir-NHCOCH2CHRHR′OCH3, while the spectrum in
CD3COCD3 shows two signals for the two protons of the
enol form, Ln-Ir-NdC(OH)CHâHâ′CHRHR′OCH3 (4a E)9
(Figure 3c,d and Supporting Information). A similar
observation was previously reported for (PMe3)Cp*Ir-
CHRHR′CHâHâ′-t-Bu that shows four signals in C6D6.10
Separate experiments have been carried out to un-
derstand the nature of the formation of di-deuterio
complex 4a -d 2 from the reaction of 1a with NaOD and
CH3OD. It has been found that the R-proton of CH2d
CHCN in 1a is completely replaced by deuterium to give
Ln-Ir-NCCDdCH2 (1a -d 1) when the slurry of 1a was
stirred in D2O. It has been found that the H/D exchange
does not occur between OD-/CH3OD and Ir-NHCOCH2-
CH2OCH3 (4a ). It is, therefore, likely that 1a -d 1 (Ln-
Ir-NCCDdCH2) is formed by the H/D exchange be-
tween 1a and OD-/CH3OD before the addition of OD-
and CH3OD to CH2dCHCN of 1a in the presence of
NaOD and CH3OD. It has been known that deprotona-
A relevant and interesting observation has been made
during this investigation. The protons of CH3CN in [Ln-
Ir(NCCH3)]+ (A)3 are also readily replaced by deuterium
in the reactions of A with D2O and CH3OD to give [Ln-
Ir(NCCD3)]+ (A-d 3) and [Ln-Ir-NDdC(OCH3)CD3]+
(B-d 4), respectively (Scheme 1). The H/D exchange,
however, does not occur between CH3OD and CH3 of
[Ln-Ir-NHdC(OCH3)CH3]+ (B)3 (which is obtained
from the reaction of A with CH3OH) and between
CH3OH and CD3 of [Ln-Ir-NDdC(OCH3)CD3]+ (B-d 4)
(which is obtained from the reaction of A with CH3OD)
(see Scheme 1).
The compound 4b has been also unequivocally char-
acterized by detailed spectral (1H, 13C NMR, 1H, 1H-2D
COSY, 1H, 13C-2D HETCOR, IR) and elemental analysis
data (see Supporting Information). Production of the
ethoxo amide H2NCOCH2CH2OCH2CH3 (5b) from the
reaction of 4b with aqueous HCl (eq 2) also supports
the ethoxo amido moiety, Ir-NHCOCH2CH2OCH2CH3
in 4b.
It is interesting to find that OH- always selectively
attacks the nitrile group (NtC-) of 1a , while ROH
selectively attacks the olefinic (-CHdCH2) group. No
experimental evidence has been obtained for the addi-
tion of CH3OH to the -CtN group of 1a to give imino-
ether complexes ([Ln-Ir-NHdC(OCH3)CHdCH2]+ or
(9) It has been suggested that amido complexes exist mainly as the
enol form isomers, M-NdC(OH)R, in a polar solvent such as acetone,
while the keto form isomer, M-NHCOR, is the predominant species
in a nonpolar solvent such as benzene. See refs 3 and 6c.
(10) Bergman, R. G.; Golden, J . T.; Peterson, T. H. Organometallics
1999, 18, 2005, and see references therein for related NMR spectral
data.

4046 Organometallics, Vol. 19, No. 20, 2000
Chin et al.
Sch em e 1
for 6 to isomerize to the enol form Ln-Ir-NdC(OH)CH2-
CH2NR2 (6E) in polar solvents. In fact, a set of small
signals are seen in the 1H NMR spectrum of 6a in CDCl3
and assigned to those of the enol form (6a E) of 6a .
Rea ction of [Cp *Ir (η3-CH2CHCHP h )(NCCHd
CH2)]+ (1a ) w ith HN(CH3)2 a n d CH3OH. The reaction
of 1a with HN(CH3)2 and CH3OH yields the amino
imino-ether complex [Ln-Ir-NHdC(OCH3)CH2CH2N-
1
(CH3)2]OTf (8) (eq 5). The H NMR spectrum of 8 shows
three singlets at δ 1.51 (15H), 2.29 (6H), and 4.09 (3H)
that are unequivocally assigned to the methyl protons
of Cp* (C5(CH3)5), N(CH3)2, and C(OCH3), respectively.
The signal due to NdC at δ 179.7 in the 13C NMR
spectrum and medium IR absorption at 1637 cm-1 due
to νNdC (and the absence of a strong absorption due to
[Ln-Ir-NHdC(OCH3)CH2CH2OCH3]+) in the presence
of OH-. In the absence of OH-, however, CH3OH seems
to attack both the -CtN and -CHdCH2 groups of 1a
in the presence of Na2CO3 to give unknown Ir complex-
(es).
Complex 4a is also obtained from the reaction of the
3-methoxo propionitrile complex [Ln-Ir-NtCCH2CH2-
OCH3]+ (1c) with OH- but not from the reaction of 2a
with CH3OH in the presence of OH- (eq 3). It is,
therefore, likely that the addition of CH3OH to the
olefinic group of CH2dCHCN in 1a is followed by the
OH- addition to the nitrile group in the formation of
4a (eq 2).
ν
CdO at ∼1600 cm-1) support the imino moiety in 8. The
Ir-NHdC(OCH3)CH2CH2N(CH3)2 unit in 8 is also
supported by the quantitative production of the ester
CH3OCOCH2CH2N(CH3)2 (9) from the hydrolysis of 8
(eq 5).
The addition of HN(CH3)2 to the nitrile group of 1a
has not been observed in the presence of both CH3OH
and HN(CH3)2. On the other hand, HN(CH3)2 is readily
added to the nitrile of 1c to give the methoxo amidine
complex [Ln-Ir-NHdC(N(CH3)2)CH2CH2OCH3)]OTf (10)
(eq 6). It is well established that amines are added to
saturated nitriles coordinated to metal to give amidine
complexes.3 Complex 10 has been unambiguously char-
acterized by detailed NMR spectral and elemental
analysis data (see Supporting Information) compared
with those of well-identified amidine complexes.3
It should be mentioned that addition of alcohols to
the olefinic group of 1b has not been observed in the
reaction of 1b with alcohols (CH3OH, C2H5OH) in the
presence of OH- at room temperature.
R ea ct ion s of [Cp *Ir (η3-CH 2CH CH P h )(NCCHd
CH2)]+ (1a ) w ith P r otic Am in es in th e P r esen ce of
OH-. Amino amido complexes Ln-Ir-NHCOCH2CH2-
NR2 (6, R2 ) (CH3)2 (a ), (CH3)(H) (b)) have been
obtained from the reactions of 1a with HNR2 in the
presence of OH- (eq 4) and unambiguously character-
ized by spectral and elemental analysis data.
For example, the 1H NMR spectrum of 6a in C6D6
clearly shows all the signals due to the protons of η3-
CHHCHCHPh and CH2CH2N(CH3)2. The signal at δ
175.7 in the 13C NMR spectrum and strong IR absorp-
tion at 1599 cm-1 are assigned to CdO and νCdO
,
respectively. Acidification of 6 with aqueous HCl pro-
duces quantitative amounts of the amino amides H2-
NCOCH2CH2NR2 (7), which supports the identification
of the amino amido complexes, 6. As observed and
discussed above for complex 2a and 4a , it is also possible
In summary, it is noteworthy that the addition of OH-
and alcohols or protic amines to the NtC- and -CHd
CH2 groups in 1a is evidently regioselective. Hydroxide

CH2dCHCN Coordinated to Cp*Ir(η3-CH2CHCHPh)
Organometallics, Vol. 19, No. 20, 2000 4047
(NCCH)CH2). IR (KBr, cm-1): 2259 (w, νCtN). Anal. Calcd for
ion has a priority of attacking the NtC- group over
CH3OH and HN(CH3)2, whereas HN(CH3)2 has priority
of attackingthe -CHdCH2 group over OH- and CH3-
OH. It may be mentioned that no report, to the best of
our knowledge, has been made for an addition of OH-
and ROH or HNR2, and CH3OH and HN(CH3)2, respec-
tively, to both nitrile (NtC-) and olefinic (-CHdCH-)
groups of coordinated unsaturated nitriles.
C
23H27O3NSF3Ir: C, 42.71; H, 4.21; N, 2.17. Found: C, 42.91;
H, 4. 26; N, 2.17.
Syn t h esis of [Cp *Ir (η3-CH 2CH CH P h )(NtCC(CH 3)d
CH2)]OTf (1b). This compound was prepared in the same
manner as described above for 1a using the same amounts of
reactants. The yield was 90% based on Cp*Ir(η3-CH2CHCHPh)-
(NtCC(CH3)dCH2)]OTf. 1H NMR (CDCl3): δ 1.57 (s, 15H, CH3
of Cp*), 2.10 (s, 3H, C(CH3)dCH2), 2.44 (d, 1H, J ) 10.0 Hz,
CHHCHCHPh), 3.45 (d, 1H, J ) 6.5 Hz, CHHCHCHPh), 4.11
(d, 1H, J ) 10.0 Hz, CH2CHCHPh), 5.05 (dt, 1H, J ) 6.5, 10.0
Hz, CH2CHCHPh), 6.09 (d, 1H, J ) 1.0 Hz, C(CH3)dCHH),
6.16 (d, 1H, J ) 1.0 Hz, C(CH3)dCHH), 7.18-7.37 (m, 5H,
C6H5). 13C NMR (CDCl3): δ 8.0 (CH3 of Cp*), 20.3 (C(CH3)d
CH2), 43.6 (CH2CHCHPh), 65.4 (CH2CHCHPh), 79.4 (CH2C-
HCHPh), 94.6 (ring C of Cp*), 115.2 (C(CH3)dCH2), 122.2,
126.0, 126.8, 128.9, 136.9, 137.9 (NtC, C6H5, C(CH3)dCH2).
IR (KBr, cm-1): 2296 (w, νCtN). Anal. Calcd for C24H29O3NSF3-
Ir: C, 43.63; H, 4.41; N, 2.12. Found: C, 43.91; H, 4.51; N,
2.04.
Ca t a lyt ic Act ivit y of 1a for t h e P r od u ct ion of
Am id es. That the metal complexes 2, 4, 6, and 8
dissociate the amides (3, 5, 7) and ester (9) in the
presence of H+ has led us to investigate the catalytic
activity of 1a for the production of the amides and
imino-ether. Unsaturated amide CH2dCHCONH2 is
slowly (>0.1 mol/Ir/h at 70 °C) produced from the
reaction of CH2dCHCN with H2O in the presence of 1a
and Na2CO3. Larger amounts of an ether ((NCCH2-
CH2)2O/Ir/h ) 0.9 at 70 °C) and alcohol (NCCH2CH2-
OH/Ir/h ) 2.3 at 70 °C) were also found in the reaction
mixture (see Experimental Section for detailed data).
All of these products (CH2dCHCONH2, (NCCH2CH2)2O,
NCCH2CH2OH) have been reported as the products of
the catalytic hydration of CH2dCHCN in the presence
of Pt(PEt3)3.2c Methoxo amide is also slowly ((CH3OCH2-
CH2CONH2)/Ir/h ) 0.8 at 70 °C) produced from the
reaction of CH2dCHCN with CH3OH and H2O in the
presence of Na2CO3. A much larger amount of the
methoxo nitrile ((CH3OCH2CH2CN)/Ir/h ) 39 at 70 °C)
was also found in the reaction mixture (see Experimen-
tal Section for detailed data). Neither the amino amide
(H2NCOCH2CH2N(CH3)2) nor the amino imino-ether
(NHdC(OCH3)CH2CH2N(CH3)2) has been obtained from
the reactions of excess CH2dCHCN with HN(CH3)2 and
1a in the presence of H2O and CH3OH, respectively.
Syn t h esis of [Cp *Ir (η3-CH 2CHCHP h )(NtCCH 2CH 2O-
CH3)]OTf (1c). This compound was prepared in the same
manner as described above for 1a using same amounts of
reactants. The yield was 91% based on [Cp*Ir(η3-CH2CHCHPh)-
(NtCCH2CH2OCH3)]OTf. 1H NMR (CDCl3): δ 1.59 (s, 15H,
CH3 of Cp*), 2.53 (dd, 1H, J ) 1.8, 10.5 Hz, CHHCHCHPh),
3.37 (dd, 1H, J ) 1.8, 7.0 Hz, CHHCHCHPh), 3.43 (s, 3H,
OCH3), 3.46 (t, 2H, J ) 6.0 Hz, CH2CH2OCH3), 3.73 (t, 2H, J
) 6.0 Hz, CH2CH2OCH3), 4.23 (d, 1H, J ) 10.5 Hz, CH2-
CHCHPh), 4.99 (dt, 1H, J ) 7.0, 10.5 Hz, CH2CHCHPh), 7.2-
7.4 (m, 5H, C6H5). 13C NMR (CDCl3): δ 7.8 (CH3 of Cp*), 20.6
(CH2CH2OCH3), 43.0 (CH2CHCHPh), 58.3 (CH2CH2OCH3),
64.9 (CH2CHCHPh), 66.4 (CH2CH2OCH3), 78.9 (CH2CHCHPh),
94.1 (ring C of Cp*), 122.6, 125.8, 126.5, 128.7, 137.3 (NtC,
C6H5). IR (KBr, cm-1): 2298 (w, νCtN). Anal. Calcd for C24H31O4-
NSF3Ir: C, 42.47; H, 4.60, N, 2.09. Found: C, 42.65; H, 4.54;
N, 2.01.
Syn th esis of Cp *Ir (η3-CH2CHCHP h )(NHCOCHdCH2)
(2a ). A reaction mixture of 1a (0.10 g, 0.15 mmol) in THF (10.0
mL) and NaOH (3.0 mL of 0.1 M solution in H2O, 0.3 mmol)
was stirred for 20 min at room temperature before CH2Cl2 (20
mL) was added to dissolve the product 2a precipitated during
the reaction. Excess NaOH and NaOTf were removed by
extraction with H2O (2 × 20 mL), and a pale yellow solid was
obtained by vacuum distillation of the organic layer and
recrystallized with CHCl3/n-pentane. The yield was 0.095 g
and 94% based on Cp*Ir(η3-CH2CHCHPh)(NHCOCHdCH2).
1H NMR (C6D6): δ 1.24 (s, 15H, CH3 of Cp*), 1.54 (d, 1H, J )
9.5 Hz, CHHCHCHPh), 2.90 (d, 1H, J ) 6.5 Hz, CHHCH-
CHPh), 3.65 (br, 1H, NH), 4.05 (d, 1H, J ) 9.5 Hz, CH2-
CHCHPh), 4.53 (dt, 1H, J ) 6.5, 9.5 Hz, CH2CHCHPh), 5.16
(dd, 1H, J ) 3.0, 9.5 Hz, CHdCHH), 6.23 (dd, 1H, J ) 9.5,
16.5 Hz, CH)CH2), 6.36 (dd, 1H, J ) 3.0, 16.5 Hz, CHdCHH).
13C NMR (C6D6): δ 8.3 (CH3 of Cp*), 40.6 (CH2CHCHPh), 62.5
(CH2CHCHPh), 73.6 (CH2CHCHPh), 91.9 (ring C of Cp*),
119.9 (CHdCH2), 136.8 (CH)CH2), 170.7 (CdO). IR (KBr,
Exp er im en ta l Section
Gen er a l In for m a tion . A standard vacuum system and
Schlenk type glassware were used in most of the experimental
procedures in handling metal compounds, although most of
compounds seem to be stable enough to be handled without
much precautions in air. NMR spectra were recorded on a
Varian Gemini 200, 300, or 500 spectrometer (1H, 200, 300,
or 500 MHz; 13C, 50, 75, or 125 MHz). IR spectra were
measured on a Nicholet 205 spectrophotometer. Gas chroma-
tography and mass spectra were obtained with Hewlett-
Packard HP 5890A and VG-trio 2000 instruments. Elemental
analyses were carried out with a Carlo Erba EA 1108.
Syn th esis of [Cp *Ir (η3-CH2CHCHP h )(NtCCHdCH2)]-
OTf (1a ). A 0.09 g (0.33 mmol) sample of AgOTf and two
drops of CH2dCHCN (ca. 20 mmol) were added to a CHCl3
(20 mL) solution of Cp*IrCl(η3-CH2CHCHPh)3,5 (0.15 g, 0.3
mmol), and the resulting solution was stirred at room tem-
perature for 1 h before AgCl was removed by filtration. A beige
solid was obtained by distillation of the filtrate solution under
vacuum and recrystallized in cold CHCl3/(C2H5)2O to isolate
beige microcrystals of 1a . The yield was 0.16 g and 90% based
on [Cp*Ir(η3-CH2CHCHPh)(NtCCHdCH2)]OTf. 1H NMR
(CDCl3): δ 1.60 (s, 15H, CH3 of Cp*), 2.55 (dd, 1H, J ) 2.0,
10.0 Hz, CHHCHCHPh), 3.42 (dd, 1H, J ) 2.0, 7.0 Hz,
CHHCHCHPh), 4.52 (d, 1H, J ) 10.0 Hz, CH2CHCHPh), 4.99
(dt, 1H, J ) 7.0, 10.0 Hz, CH2CHCHPh), 6.35-6.56 (m, 3H,
NCCH)CH2), 7.22-7.43 (m, 5H, C6H5). 13C NMR (CDCl3): δ
8.0 (CH3 of Cp*), 43.6 (CH2CHCHPh), 65.5 (CH2CHCHPh),
79.4 (CH2CHCHPh), 94.7 (ring C of Cp*), 106.2 (NCCHdCH2),
120.4 (NtC), 126.1, 126.9, 128.9, 137.1 (C6H5), 143.4
cm-1): 3309 (m, νNH), 1595 (s, νCdO). Anal. Calcd for C22H28
-
ONIr: C, 51.34; H; 5.48, N, 2.72. Found: C, 51.33; H, 5. 48;
N, 2.71.
1H NMR (2a , CDCl3): δ 1.51 (s, 15H, CH3 of Cp*), 1.69 (d,
1H, J ) 9.6 Hz, CHHCHCHPh), 3.15 (d, 1H, J ) 6.6 Hz,
CHHCHCHPh), 3.83 (d, 1H, J ) 9.6 Hz, CH2CHCHPh), 4.09
(br, 1H, NH), 4.81 (dt, 1H, J ) 6.6, 9.6 Hz, CH2CHCHPh),
5.20 (dd, 1H, J ) 2.1, 10.0 Hz, CHdCHH), 5.93 (dd, 1H, J )
2.1, 17.0 Hz, CHdCHH), 6.27 (dd, 1H, J ) 10.0, 17.0 Hz, CHd
CH2), 7.04-7.59 (m, 5H, C6H5). 13C NMR (2a , CDCl3): δ 7.90
(CH3 of Cp*), 40.5 (CH2CHCHPh), 60.6 (CH2CHCHPh), 73.1
(CH2CHCHPh), 91.4 (ring C of Cp*), 119.1 (CHdCH2), 124.4
126.6, 127.6 and 140.4 (C6H5), 135.9 (CHdCH2), 170.5(Cd
O).1H NMR (2a E, CDCl3): δ 1.49 (s, 15H, CH3 of Cp*), 1.91
(d, 1H, J ) 9.6 Hz, CHHCHCHPh), 3.20 (d, 1H, J ) 6.3 Hz,

4048 Organometallics, Vol. 19, No. 20, 2000
Chin et al.
CHHCHCHPh), 3.55 (d, 1H, J ) 9.6 Hz, CH2CHCHPh), 4.62
(br, 1H, OH), 5.02 (dt, 1H, J ) 6.3, 9.6 Hz, CH2CHCHPh), 5.45
(dd, 1H, J ) 2.4, 10.0 Hz, CHdCHH), 6.26 (dd, 1H, J ) 2.4,
17.4 Hz, CHdCHH), 6.53 (dd, 1H, J ) 10.0, 17.4 Hz, CHd
CH2).13C NMR (2a E, CDCl3): δ 7.81 (CH3 of Cp*), 41.5 (CH2-
CHCHPh), 61.9 (CH2CHCHPh), 75.1 (CH2CHCHPh), 92.0
(ring C of Cp*), 123.2 (CHdCH2), 125.0, 127.0, 128.2 and 139.5
(C6H5), 133.8 (CHdCH2), 171.3 (CdN).1H NMR (2a E, CD3-
COCD3): δ 1.54 (s, 15H, CH3 of Cp*), 1.67 (d, 1H, J ) 9.5 Hz,
CHHCHCHPh), 3.15 (d, 1H, J ) 6.5 Hz, CHHCHCHPh), 4.45
(br, 1H, OH), 3.76 (d, 1H, J ) 10.0 Hz, CH2CHCHPh), 5.02
(dt, 1H, J ) 6.5, 10.0 Hz, CH2CHCHPh), 5.07 (dd, 1H, J )
3.0, 10.0 Hz, CHdCHH), 5.83 (dd, 1H, J ) 3.0, 17.0 Hz, CHd
CHH), 6.37 (dd, 1H, J ) 10.0, 17.0 Hz, CHdCH2).13C NMR
(2a E, CD3COCD3): δ 3.1 (CH3 of Cp*), 35.7 (CH2CHCHPh),
56.5 (CH2CHCHPh), 68.7 (CH2CHCHPh), 87.3 (ring C of Cp*),
113.5 (CHdCH2), 120.2, 122.9, 123.3, 137.0 (C6H5), 132.5 (CHd
CH2), 165.3 (CdN).
Syn th esis of Cp *Ir (η3-CH2CHCHP h )(NHCOC(CH3)d
CH2) (2b). This compound was prepared in the same manner
as described above for 2a using the same amounts of reactants.
The yield was 93% based on Cp*Ir(η3-CH2CHCHPh)(NHCOC-
(CH3)dCH2). 1H NMR (C6D6): δ 1.50 (s, 15H, CH3 of Cp*), 1.66
(d, 1H, J ) 9.5 Hz, CHHCHCHPh), 1.92 (s, 3H, C(CH3)dCH2),
3.15 (d, 1H, J ) 6.5 Hz, CHHCHCHPh), 3.77 (d, 1H, J ) 9.5
Hz, CH2CHCHPh), 4.27 (br, 1H, NH), 4.80 (dt, 1H, J ) 6.5,
9.5 Hz, CH2CHCHPh), 4.94 (d, 1H, J ) 1.0 Hz, C(CH3)dCHH),
5.34 (d, 1H, J ) 1.0 Hz, C(CH3)dCHH). 13C NMR (C6D6): δ
8.3 (CH3 of Cp*), 20.1 (C(CH3)dCH2), 40.9 (CH2CHCHPh), 61.3
(CH2CHCHPh), 73.5 (CH2CHCHPh), 91.8 (ring C of Cp*),
114.2 (C(CH3)dCH2), 145.7 (C(CH3)dCH2), 174.6 (CdO). IR
(KBr, cm-1): 3407 (w, νNH), 1588 (s, νCdO). Anal. Calcd for
C6H5). 1H NMR (4a E, CD3COCD3): δ 1.58 (s, 15H, CH3 of Cp*),
1.67 (d, 1H, J ) 9.5 Hz, CHHCHCHPh), 2.41 (t, 2H, J ) 6.0
Hz, CH2CH2OCH3), 3.16 (d, 1H, J ) 6.5 Hz, CHHCHCHPh),
3.28 (s, 3H, CH2CH2OCH3), 3.58 (m, 2H, CH2CH2OCH3), 3.77
(d, 1H, J ) 9.5 Hz, CH2CHCHPh), 4.16 (br, 1H, OH), 5.03 (dt,
1H, J ) 6.5, 9.5 Hz, CH2CHCHPh), 7.00-7.45 (m, 5H, C6H5).
13C NMR (4a E, CD3COCD3): δ 8.05 (CH3 of Cp*), 41.6 (CH2-
CH2OCH3), 41.8 (CH2CHCHPh), 58.8 (CH2CH2OCH3), 62.3
(CH2CHCHPh), 72.2 (CH2CH2OCH3), 74.5 (CH2CHCHPh),
92.8 (ring C of Cp*), 125.1, 127.0, 128.2 and 139.5 (C6H5),
170.3(CdN). HETCOR (4a , 1H (500 MHz) f 13C (126 MHz),
CDCl3): δ 2.46 f 40.3; δ 3.35 f 58.1; δ 3.65 f 70.6
(Supporting Information).
Syn t h esis of Cp *Ir (η3-CH2CH CH P h )(NH COCD2CH 2-
OCH3) (4a -d 2). This compound was prepared in the same
manner as described above for 4a using 1a (0.15 mmol), CH3-
OD (10 mL), and NaOD (3.0 mL of 0.1 M solution in D2O, ca.
0.3 mmol). Excess NaOD and NaOTf were removed by dis-
solving in H2O, which presumably replaced the deuterium
bound to the nitrogen (Ir-NDCOCD2CH2OCH3) with hydro-
gen.
Rea ction of [Cp *Ir (η3-CH2CHCHP h )(NtCCHdCH2)]-
OTf (1a ) w ith D2O to P r od u ce [Cp *Ir (η3-CH2CHCHP h )-
(NtCCDdCH2)]OTf (1a -d 1). A slurry of 1a (0.05 g) in D2O
(3 mL) was stirred at 50 °C for 15 h and cooled to room
temperature. Pale yellow solid was obtained by filtration and
dried under vacuum. 1H NMR spectrum clearly showed a
significant decrease (by one-third) in the integration of those
signals due to NCCHdCH2 in δ 6.35-6.56 compared with
those of 1a (see Supporting Information). The 13C NMR
spectrum (1H decoupled) of 1a -d 1 also showed that the signal
due to the R-carbon of the nitrile (Ir-NCCDdCH2) at δ 106.2
ppm is broadened due to the coupling with deuterium (Sup-
porting Information).
C
23H30ONIr: C, 52.25; H, 5.72; N, 2.65. Found: C, 52.23; H,
5. 68; N, 2.61.
Deu tr a tion of CH3CN in [Cp *Ir (η3-CH2CHCHP h )(NC-
CH3)]+ (A) a n d Rela ted Rea ction s in Sch em e 1. Compound
A and its methanol adduct [Cp*Ir(η3-CH2CHCHPh)(NHd
C(OCH3)CH3)]+ (B) were prepared by the literature methods.3
Deuterium-containing compounds A-d 3 and B-d 4 were pre-
pared by the same manner as described in the literature3 for
A using CH3OD and for 1a -d 1 (see above), respectively, and
Syn t h esis of Cp *Ir (η3-CH2CH CH P h )(NH COCH2CH 2-
OCH3) (4a ). A reaction mixture of 1a (0.1 g, 0.15 mmol) in
CH3OH (10.0 mL) and NaOH (3.0 mL of 0.1 M solution in H2O,
ca. 0.3 mmol) was stirred for 20 min at room temperature
before CH2Cl2 (20 mL) was added to dissolve the product 4a
precipitated during the reaction. Excess NaOH and NaOTf
were removed by extraction with H2O, and a pale yellow solid
was obtained by distillation of the organic layer under vacuum
and recrystallized with CHCl3/n-pentane. The yield was 0.076
g and 93% based on Cp*Ir(η3-CH2CHCHPh)(NHCOCH2CH2-
1
identified by H NMR spectral measurements.
Syn th esis of Cp *Ir (η3-CH2CHCHP h )(NHCOCH2CH2O-
CH2CH3) (4b). This compound was prepared in the same
manner as described above for 4a using the same amounts of
reactants. The yield was 85% based on Cp*Ir(η3-CH2CHCHPh)-
1
OCH3). H NMR (C6D6): δ 1.32 (s, 15H, CH3 of Cp*), 1.65 (d,
1H, J ) 9.0 Hz, CHHCHCHPh), 2.56 (t, 2H, J ) 6.3 Hz, CH2-
CH2OCH3), 2.96 (d, 1H, J ) 6.5 Hz, CHHCHCHPh), 3.17 (s,
3H, CH2CH2OCH3), 3.67 (m, 1H, CH2CHHOCH3), 3.79 (m, 1H,
CH2CHHOCH3), 4.08 (d, 1H, J ) 9.0 Hz, CH2CHCHPh), 4.61
(dt, 1H, J ) 9.0, 6.3 Hz, CH2CHCHPh). 13C NMR (C6D6): δ
8.3 (CH3 of Cp*), 40.6 (CH2CH2OCH3), 40.9 (CH2CHCHPh),
58.2 (CH2CH2OCH3), 62.3 (CH2CH2CHPh), 71.5 (CH2CH2-
OCH3), 73.4 (CH2CHCHPh), 91.8 (ring C of Cp*), 174.4 (Cd
O). IR (KBr, cm-1): 3380 (w, νN-H), 1612 (s, νCdO). Anal. Calcd
for C23H32O2NIr: C, 50.53; H, 5.90, N, 2.56. Found: C, 50.32;
H, 5. 81; N, 2.49.
1H NMR (4a , CDCl3): δ 1.49 (s, 15H, CH3 of Cp*), 1.67 (d,
1H, J ) 9.5 Hz, CHHCHCHPh), 2.46 (t, 2H, J ) 6.0 Hz, CH2-
CH2OCH3), 3.14 (d, 1H, J ) 6.5 Hz, CHHCHCHPh), 3.35 (s,
3H, CH2CH2OCH3), 3.65 (m, 2H, CH2CH2OCH3), 3.78 (d, 1H,
J ) 9.5 Hz, CH2CHCHPh), 4.03 (br, 1H, NH), 4.80 (dt, 1H, J
) 6.5, 9.5 Hz, CH2CHCHPh), 7.00-7.45 (m, 5H, C6H5). 13C
NMR (4a , CDCl3): δ 8.02 (CH3 of Cp*), 40.3 (CH2CH2OCH3),
40.5(CH2CHCHPh), 58.1 (CH2CH2OCH3), 60.8 (CH2CHCHPh),
70.6 (CH2CH2OCH3), 73.0 (CH2CHCHPh), 91.5 (ring C of Cp*),
124.5, 126.6, 127.8 and 140.8 (C6H5), 174.7 (CdO). 1H NMR
(4a E, CDCl3): δ 1.42 (s, 15H, CH3 of Cp*), 1.84 (d, 1H, J )
9.5 Hz, CHHCHCHPh), 2.55 (t, 2H, J ) 6.0 Hz, CH2CH2OCH3),
3.25 (d, 1H, J ) 6.5 Hz, CHHCHCHPh), 3.38 (s, 3H, CH2CH2-
OCH3), 3.65 (m, 2H, CH2CH2OCH3), 4.49 (br, 1H, OH), 4.98
(dt, 1H, J ) 6.5, 9.5 Hz, CH2CHCHPh), 7.00-7.45 (m, 5H,
1
(NHCOCH2CH2OCH2CH3). H NMR (C6D6): δ 1.12 (t, 3H, J
) 7.0 Hz, OCH2CH3), 1.33 (s, 15H, CH3 of Cp*), 1.66 (d, 1H, J
) 9.0 Hz, CHHCHCHPh), 2.58 (t, 2H, J ) 6.3 Hz, CH2CH2-
OCH2CH3), 2.97 (d, 1H, J ) 6.9 Hz, CHHCHCHPh), 3.35 (q,
2H, J ) 7.0 Hz, OCH2CH3), 3.67 (br, 1H, NH), 3.73 (m, 1H,
CH2CHHOCH2CH3), 3.85 (m, 1H, CH2CHHOCH2CH3), 4.09 (d,
1H, J ) 9.0 Hz, CH2CHCHPh), 4.62 (dt, 1H, J ) 9.0, 6.9 Hz,
CH2CHCHPh). 13C NMR (C6D6): δ 8.4 (CH3 of Cp*), 15.6
(OCH2CH3), 40.5, 41.0 (CH2CH2OCH2CH3, CH2CHCHPh), 62.2
(CH2CHCHPh), 66.1 (OCH2CH3), 69.4 (CH2CH2OCH2CH3),
73.3 (CH2CHCHPh), 91.8 (ring C of Cp*), 174.9 (CdO). IR
(KBr, cm-1): 3281 (w, νN-H), 1610 (s, νCdO). Anal. Calcd for
C
24H34O2NIr: C, 51.41; H, 6.11; N, 2.50. Found: C, 51.33; H,
6.08; N, 2.61.
1H NMR (4b, CDCl3): δ 1.06 (t, 3H, J ) 7.0 Hz, OCH2CH3),
1.38 (s, 15H, CH3 of Cp*), 1.54 (d, 1H, J ) 10.0 Hz, CHHCH-
CHPh), 2.36 (t, 2H, J ) 6.5 Hz, CH2CH2O CH2CH3), 3.00 (d,
1H, J ) 6.5 Hz, CHHCHCHPh), 3.36 (q, 2H, J ) 7.0 Hz, OCH2-
CH3), 3.56 (m, 2H, CH2CH2OCH2CH3), 3.64 (d, 1H, J ) 10.0
Hz, CH2CHCHPh), 3.96 (br, 1H, NH), 4.66 (dt, 1H, J ) 6.5,
10.0 Hz, CH2CHCHPh), 6.96-7.40 (m, 5H, C6H5). 13C NMR
(4b, CDCl3): δ 8.00 (CH3 of Cp*), 14.9 (OCH2CH3), 40.4 (CH2-
CH2OCH2CH3), 40.5 (CH2CHCHPh), 60.7 (CH2CHCHPh), 65.6
(OCH2CH3), 68.4 (CH2CH2OCH2CH3), 73.0 (CH2CHCHPh),
91.4 (ring C of Cp*), 124.4, 126.6, 127.7 and 140.8 (C6H5), 174.9

CH2dCHCN Coordinated to Cp*Ir(η3-CH2CHCHPh)
Organometallics, Vol. 19, No. 20, 2000 4049
(CdO). HETCOR (4b, 1H (500 MHz) f 13C (126 MHz),
CDCl3): δ 1.06 f 14.9; δ 2.36 f 40.4; δ 3.36 f 65.6; δ 3.56 f
68.4 (Supporting Information).
was washed with cold CHCl3 (3 mL) to obtain relatively pure
H2NCOCHdCH2 (3a ). 1H NMR (CDCl3): δ 5.58 (br, 2H, NH2),
5.73 (dd, 1H, J ) 1.5, 10.2 Hz, CHdCHH), 6.15 (dd, 1H, J )
10.2, 17.2 Hz, CH)CH2), 6.30 (dd, 1H, J ) 1.5, 17.2 Hz, CHd
CHH). Mass: M+ at m/z 71. The iridium compound Cp*IrCl-
(η3-CH2CHCHPh) in the CHCl3 layer was extracted by diethyl
ether (10 mL), isolated by evaporation of the solvent, and
Syn th esis of Cp *Ir (η3-CH2CHCHP h )(NHCOCH2CH2N-
(CH3)2) (6a ). This compound was prepared in the same
manner as described above for 4a using 0.15 mmol of 1a , HN-
(CH3)2 (1.0 mL of 40 wt % solution in H2O), and NaOH (3.0
mL of 0.1 M in H2O, 0.32 mmol). The yield was 87% based
on Cp*Ir(η3-CH2CHCHPh)(NHCOCH2CH2N(CH3)2).1H NMR
(C6D6): δ 1.39 (s, 15H, CH3 of Cp*), 1.76 (d, 1H, J ) 9.5 Hz,
CHHCHCHPh), 2.16 (s, 6H, N(CH3)2), 2.54 (t, 2H, J ) 7.0 Hz,
CH2CH2N(CH3)2), 2.69 (m, 2H, CH2CH2N(CH3)2), 3.06 (d, 1H,
1
identified by H NMR measurement.3
Data for H2NCOC(CH3)dCH2 (3b) as follows. 1H NMR
(CDCl3): δ 1.98 (s, 3H, CH3), 5.42 (s, 1H, C(CH3)dCHH), 5.62
(br, 2H, NH2), 5.77 (s, 1H, C(CH3)dCHH). Mass: M+ at m/z
85.
Data for H2NCOCH2CH2OCH3 (5a ) as follows.1H NMR
(CDCl3): δ 2.50 (t, 2H, J ) 5.3 Hz, CH2CH2OCH3), 3.38 (s,
3H, OCH3), 3.64 (t, 2H, J ) 5.3 Hz, CH2CH2OCH3), 5.93, 6.41
(br, 2H, NH2). Mass: M+ at m/z 103.
J
) 6.5 Hz, CHHCHCHPh), 4.16 (d, 1H, J ) 9.5 Hz,
CH2CHCHPh,), 4.17 (br, 1H, NH), 4.68 (dt, 1H, J ) 9.5, 6.5
Hz, CH2CHCHPh). 13C NMR (C6D6): δ 8.3 (CH3 of Cp*), 38.1
(CH2CH2N(CH3)2), 40.5 (CH2CHCHPh), 45.3 (CH2CH2N-
(CH3)2), 58.0 (CH2CH2N(CH3)2), 62.3 (CH2CHCHPh), 73.3
(CH2CHCHPh), 91.7 (ring C of Cp*), 175.7 (CdO). IR (KBr,
Data for H2NCOCH2CH2OCH2CH3 (5b) as follows.1H NMR
(CDCl3): δ 1.23 (t, 3H, J ) 7.0 Hz, OCH2CH3), 2.50 (t, 2H, J
) 6.0 Hz, CH2CH2OCH2CH3), 3.54 (q, 2H, J ) 7.0 Hz, OCH2-
CH3), 3.69 (t, 2H, J ) 6.0 Hz, CH2CH2OCH2CH3), 5.33, 6.33
(br, 2H, NH2). Mass: M+ at m/z 117.
cm-1): 3381 (w, νNH), 1599 (s, νCdO). Anal. Calcd for C24H35
-
ON2Ir: C, 51.50; H, 6.30; N, 5.00. Found: C; 51.41; H, 6.31;
N, 4.99.
1
Syn t h esis of Cp *Ir (η3-CH2CH CH P h )(NH COCH2CH 2-
NHCH3) (6b). This compound was prepared in the same
manner as described above for 4a using 0.15 mmol of 1a , H2-
NCH3 (1.0 mL of 40 wt % solution in H2O), and NaOH (3.0
mL of 0.1 M in H2O, ca. 0.32 mmol). The yield was 84% based
on Cp*Ir(η3-CH2CHCHPh)(NHCOCH2CH2NHCH3). 1H NMR
(C6D6): δ 1.45 (s, 15H, CH3 of Cp*), 1.77 (d, 1H, J ) 9.5 Hz,
CHHCHCHPh), 2.51 (s, 3H, NHCH3), 2.60 (t, 2H, J ) 6.5 Hz,
CH2CH2NHCH3), 3.02 (m, 2H, CH2CH2NHCH3), 3.11 (d, 1H,
J ) 6.5 Hz, CHHCHCHPh), 3.87 (br, 1H, NH), 4.19 (d, 1H, J
) 9.5 Hz, CH2CHCHPh), 4.74 (dt, 1H, J ) 9.5, 6.5 Hz,
CH2CHCHPh). 13C NMR (C6D6): δ 8.5 (CH3 of Cp*), 36.6 (CH2-
CH2NHCH3), 40.1 (CH2CH2NHCH3), 41.5 (CH2CHCHPh), 49.9
(CH2CH2NHCH3), 61.3 (CH2CHCHPh), 73.5 (CH2CHCHPh),
91.9 (ring C of Cp*), 176.1 (C)O). IR (KBr, cm-1): 3381 (w,
Data for H2NCOCH2CH2N(CH3)2 (7a ) as follows. H NMR
(D2O): δ 2.70 (t, 2H, J ) 6.9 Hz, CH2CH2N(CH3)2), 2.80 (s,
6H, N(CH3)2), 3.31 (t, 2H, CH2CH2N(CH3)2). Mass: M+ at m/z
116.
Data for H2NCOCH2CH2NHCH3 (7b) as follows.1H NMR
(D2O): δ 2.75 (t, 2H, J ) 6.6 Hz, CH2CH2N(CH3)2), 2.77 (s,
3H, NHCH3), 3.31 (t, 2H, J ) 6.6 Hz, CH2CH2NHCH3). Mass:
M+ at m/z 102.
1
Data for CH3OCOCH2CH2N(CH3)2 (9) as follows. H NMR
(CDCl3): δ 2.92 (s, 6H, N(CH3)2), 2.93 (t, 2H, J ) 6.6 Hz, CH2-
CH2N(CH3)2), 3.43 (t, 2H, J ) 6.6 Hz, CH2CH2N(CH3)2), 3.76
(s, 3H, OCH3). Mass: M+ at m/z 131.
Syn th esis of [Cp *Ir (η3-CH2CHCHP h )(NHdC(N(CH3)2)-
CH2CH2OCH3)]OTf (10). This compound has been prepared
in the same manner as described for the addition of amines
to the saturated nitriles coordinated to [Cp*Ir(η3-CH2CH-
CHPh)]+ in the previous report.3 The yield was 89% based on
[Cp*Ir(η3-CH2CHCHPh)(NHdC(N(CH3)2)CH2CH2OCH3)]-
OTf. 1H NMR (CDCl3): δ 1.48 (s, 15H, CH3 of Cp*), 2.08 (d,
1H, J ) 9.6 Hz, CHHCHCHPh), 3.00 (t, 2H, J ) 7.0 Hz, CH2-
CH2OCH3), 3.17 (s, 6H, HNdC(N(CH3)2)), 3.34 (s, 3H, CH2-
CH2OCH3), 3.46 (d, 1H, J ) 6.5 Hz, CHHCHCHPh), 3.60 (m,
2H, CH2CH2OCH3), 3.81 (d, J ) 9.6 Hz, CH2CHCHPh), 5.04
(dt, 1H, J ) 9.6, 6.5 Hz, CH2CHCHPh), 5.80 (br, 1H, NH),
7.19-7.37 (m, 5H, C6H5). 13C NMR (CDCl3): δ 8.15 (CH3 of
Cp*), 35.2 (CH2CH2OCH3), 39.9 (N(CH3)2), 43.9 (CH2CHCHPh),
58.7 (OCH3), 62.5 (CH2CHCHPh), 68.4 (CH2CH2OCH3), 77.7
(CH2CHCHPh), 92.8 (ring C of Cp*), 125.9, 126.2, 128.8 and
138.9 (C6H5), 167.6 (NdC). IR (KBr, cm-1): 3312 (w, νNH), 1584
(s, νCdN), 1029, 1152 and 1272 (s, OTf). Anal. Calcd for
C26H38O4N2F3SIr: C, 43.14; H, 5.29; N, 3.87. Found: C, 43.06;
H, 5.12; N, 3.81.
νNH), 1599 (s, νCdO). Anal. Calcd for C23H33ON2Ir: C, 50.62; H,
6.09; N, 5.13. Found: C; 50.49, H, 6.01; N, 4.99.
Syn th esis of [Cp *Ir (η3-CH2CHCHP h )(NHdC(OCH3)-
CH2CH2N(CH3)2)]OTf (8). A reaction mixture of 1a (0.10 g,
0.15 mmol) and HN(CH3)2 (5 mL of 2.0 M in CH3OH) was
stirred at 0 °C for 1 h and distilled under vacuum to obtain
yellow solid, which was recrystallized with cold CHCl3/
(C2H5)2O to obtain pale yellow microcrystals of 8. The yield
was 0.097 g and 89% based on [Cp*Ir(η3-CH2CHCHPh)(HNd
C(OCH3)CH2CH2N(CH3)2)]OTf. 1H NMR (CDCl3): δ 1.51 (s,
15H, CH3 of Cp*), 1.83 (d, 1H, J ) 10.0 Hz, CHHCHCHPh),
2.29 (s, 6H, N(CH3)2), 2.74 (m, 2H, CH2CH2N(CH3)2), 2.96 (t,
2H, J ) 6.5 Hz, CH2CH2N(CH3)2), 3.30 (d, 1H, J ) 7.0 Hz,
CHHCHCHPh), 3.48 (d, 1H, J ) 10.0 Hz, CH2CHCHPh), 4.09
(s, 3H, HNdC(OCH3)CH2), 4.90 (dt, 1H, J ) 7.0, 10.0 Hz,
CH2CHCHPh), 10.2 (br, 1H, NHdC). 13C NMR (CDCl3): δ 8.3
(CH3 of Cp*), 26.6 (CH2CH2N(CH3)2), 41.6 (CH2CHCHPh), 44.2
(N(CH3)2), 55.2 (CH2CH2N(CH3)2), 57.1 (OCH3), 62.6 (CH2-
CHCHPh), 75.7 (CH2CHCHPh), 92.8 (ring C of Cp*), 125.9,
126.1, 128.8, 139.3 (C6H5), 179.7 (CdN). IR (KBr, cm-1): 1637
(s, νCdN). Anal. Calcd for C26H38O4N2F3SIr: C, 43.14; H, 5.29;
N, 3.87. Found: C, 42.92; H, 5.50; N, 3.89.
Ca ta lytic Rea ction s of CH 2dCHCN w ith H2O, CH3OH,
or NH(CH3)2 in th e P r esen ce of 1a . All these reactions have
been carried out in the same manner as described below for
the reaction of CH2dCHCN with H2O in the presence of 1a
and Na2CO3. A 0.05 mmol sample of 1a , 10.0 mmol of CH2d
CHCN, and 50 mmols each of H2O, Na2CO3, CH3OH, and NH-
(CH3)2 were used for all catalytic reactions. The reaction
mixture of 1a , CH2dCHCN, H2O, and Na2CO3 was stirred at
70 °C for 5 h in a bomb reactor under N2 before it was cooled
on an ice bath. A portion of the reaction mixture was analyzed
by GC/mass data. Reaction of NCCHdCH2 with H2O: NCCHd
CH2 (89%, 8.9 mmol), H2NCOCHdCH2 (0.2%, 0.02 mmol),
(NCCH2CH2)2O (2%, 0.2 mmol), NCCH2CH2OH (6%, 0.6
mmol). Reaction of NCCHdCH2 with CH3OH: NCCHdCH2
(2%, 0.2 mmol), NCCH2CH2OCH3 (98%, 9.8 mmol).
R ea ct ion s of 2, 4, 6, a n d 8 w it h HCl (a q u eou s) t o
P r od u ce Am id es, H2NCOCRdCH2 (3, R ) H (a ), CH3 (b)),
H2NCOCH2CH2OR (5, R ) CH3 (a), C2H5 (b)), an d H2NCOC-
H2CH2 NR2 (7, R ) (CH3)2 (a ), (CH3)(H) (b)), a n d Ester
(CH3OCOCH2CH2N(CH3)2 (9)), Resp ectively. All of these
reactions were carried out in the same manner as described
below for the reaction of 2a with HCl (aqueous). A mixture of
HCl solution (0.5 mL of 32 wt % HCl in H2O) and 2a (0.10 g,
0.19 mmol) in CHCl3 (5.0 mL) was stirred at room temperature
for 3 h, during which time the light yellow mixture turned
darker. A 3.0 mL sample of H2O was added to the reaction
mixture to extract the water-soluble amide, and the aqueous
layer was distilled under vacuum to obtain a white solid, which
X-r a y Str u ctu r a l Deter m in a tion of [Cp *Ir (η3-CH2CH-
CH P h )(NtCCHdCH2]OTf (1a ) a n d Cp *Ir (η3-CH2CH -
CHP h )(NHC(dO)CH2CH2OMe) (4a ). Crystals were grown

4050 Organometallics, Vol. 19, No. 20, 2000
Chin et al.
Ta ble 1. Deta ils of Cr ysta llogr a p h ic Da ta
Collection of th e Com p lexes 1a a n d 4a a
ite-monochromated Mo KR radiation at room temperature.
Accurate cell parameters were determined from the least-
squares fit of 24 accurately centered reflections in each selected
range. All data were collected with the ω/ 2θ scan modes and
corrected Lp effects and absorption. The structures of these
compounds were solved by Patterson’s heavy atom methods
(SHELXS-97). Details of crystallographic data collection are
listed in Table 1. Bond distances and angles, positional and
thermal parameters, and anisotropic thermal parameters have
been included in the tables of Supporting Information. Non-
hydrogen atom were refined by full-matrix least-squares
techniques (SHELXL-97). All hydrogen atoms were placed at
their geometrically calculated positions (dCH ) 0.960 Å for
methyl and 0.930 Å for aromatic) and refined riding on the
corresponding carbon atoms with isotropic thermal param-
eters. The final R1 and wR2 (R1 ) [∑|Fo| - |Fc|/|Fo| and wR2 )
1a
4a
chemical formula
fw
temp, K
cryst dimen, mm
cryst syst
space group
a, Å
C23 H27 N O3 S F3 Ir
646.72
C23H32O2NIr
546.70
293(2)
293(2)
0.4 × 0.5 × 0.5
monoclinic
P21/c
13.668(4)
12.011(2)
16.133(8)
90.00
0.3 × 0.1 × 0.6
monoclinic
P21/c
7.269(6)
15.060(5)
19.619(9)
90.00
b, Å
c, Å
R, deg.
â, deg.
111.85(3)
90.00
92.61(6)
90.00
γ, deg.
V, Å3
2548.2(15)
4
2145(2)
4
Z
F
(calc), g cm-1
1.747
1.693
µ, mm-1
5.563
6.240
2
[∑w(Fo - Fc2)2/∑w(Fo2)2]0.5) values were 0.043 and 0.1143 for
F(000)
1264
1080
1a and 0.031 and 0.079 for 4a , respectively.
radiation
wavelength
2θ max, deg
hkl range
Mo KR
Mo KR
0.7107
0.7107
50
50
Ack n ow led gm en t. The authors wish to thank the
Korea Research Foundation in the program of 1998 for
their financial support of this study.
0 e h e 16
0 e k e 14
-19 e l e 17
4545
-6 e h e 6
0 e k e 14
-3 e l e 18
2018
no. of reflns
no. of unique data
no. of obs data
(|Fo| δ 4σFo)
no. of params
scan type
R1
4317
2763
1989
1655
Su p p or tin g In for m a tion Ava ila ble: Tables of bond
distances and angles, positional and thermal parameters, and
307
ω/2θ
0.043
0.1143
1.063
244
1
anisotropic thermal parameters for complexes 1a and 4a . H
ω/2θ
0.031
0.079
1.193
(for 1a , 1a -d 1, 2a , 2a E, 4a , 4a E, 10 in CDCl3, 4a , 4a -d 2 in
C6D6, and 4a E in CD3COCD3), 13C (for 1a , 1a -d 1, 2a , 2a E in
wR2
GOF
1
1
CDCl3,), H, H-2D COSY (for 4a , 4b), and 1H, 13C-2D HET-
COR (for 4a , 4b). This material is available free of charge via
the Internet at http://pubs.acs.org.
R1 ) [∑|Fo| - |Fc|/|Fo|], wR2 ) [∑w(Fo - Fc2)2/∑w(Fo2)2]0.5
.
a
2
from CHCl3 (1a ) and benzene (4a ). Diffraction data were
collected on an Enraf-Nonius CAD4 diffractometer with graph-
OM0002881