1,1-Insertion of substituted alkynes into the Ir-O bond of η2-carboxylato iridium complexes

Article abstract of DOI:10.1016/j.jorganchem.2004.11.040

Alkyl-carbonyl-iridium [Ir(CH₃)(CO)(η²-O ₂CR′)(PPh₃)₂]⁺ (1, R′ = CH₃, Ph, p-C₆H₄CH₃) react with alkynes (RC≡CH; R = Ph, p-C₆H₄

Full text of DOI:10.1016/j.jorganchem.2004.11.040

Journal of Organometallic Chemistry 690 (2005) 1306–1313
www.elsevier.com/locate/jorganchem
1,1-Insertion of substituted alkynes into the Ir–O bond of
g2-carboxylato iridium complexes
*
*
Chong Shik Chin , Hyungeui Lee , Myung Ki Lee, Soyoung Noh,
Min-Sik Eum, Seunggweon Hong
Chemistry Department, Sogang University, 1 Shinsoo-dong, Mapo-gu, Seoul 121-742, Republic of Korea
Received 12 October 2004; accepted 25 November 2004
Abstract
Alkyl-carbonyl-iridium [Ir(CH3)(CO)(g2-O2CR0)(PPh3)2]+ (1, R0 = CH3, Ph, p-C6H4CH3) react with alkynes (RC„CH; R = Ph,
p-C6H4CH3) in the presence of NEt3 to give acyl-alkynyl-iridium Ir(C(@O)CH3)(–C„CR)(g2-O2CR0)(PPh3)2 (4) which further
react with RC„CH to give alkyl-carbonyl-cis-bis(alkynyl) iridium Ir(CH3)(CO)(C„CR)2(PPh3)2 (5). cis-Bis(alkenyl)iridium com-
plexes, Ir(–CH@CH2)2(g2-O2CCH3)(PPh3)2 (6) and Ir(-CH=CHCH=CH)(g2-O2CCH3)(PPh3)2 (7) react with substituted alkynes
RC„CH (R = Ph, p-C6H4CH3, cyclohex-1-enyl) to give cis-bis(alkynyl) Ir(C„CR)2(g2-O2CCH3)(PPh3)2 (9) that further react with
RC„CH to undergo the alkyne insertion reaction into the Ir–O bond to produce iridacycles containing vinyl acetate ligands,
(–C„CR) (PPh ) (8).
Ir(C(=CHR)OC(CH3)=O)
2
3 2
ꢀ 2004 Elsevier B.V. All rights reserved.
Keywords: 1,1-Insertion; Iridium; Alkynes; Vinylidenes; M–C–O bond formation
1. Introduction
(1a) to form new Ir–C(@CH2)-O– moiety (2) and alkyl
migration to carbonyl ligand followed by formation of
Ir@C(OR)CH3 groups from reactions with HC„CH
and alcohols to produce acyl-alkoxycarbene complexes
(3) (Eq. (1)) [4]. Reactions of 1 with substituted alkynes
(RC„CH), however, give somewhat different types of
metal complexes with different types of hydrocarbyl li-
gands (see below).
Reactions of transition metals with alkynes have
been extensively investigated as they produce not only
a variety of interesting organic compounds [1] but also
metal-hydrocarbyls [2], such as metal-alkenyls, -alky-
nyls, -carbenes, and -vinylidenes which are reactive pre-
cursors as well as intermediates of various reactions.
During our studies on reactions of iridium compounds
with alkynes, we have isolated a variety of iridium
hydrocarbyls that undergo various types of C–C bond
forming reactions to produce interesting conjugated or-
ganic compounds [3]. We also found some interesting
types of reactions such as 1,1-insertion of HC„CH
into the Ir–O bond of an acetato-iridium complex
+
L
Ir
+
+
L
L
R'O
OC
HC CH
R'OH
O
O
O
HC CH
OC
H3C
O
O
Ir
Ir
H3C
H3C
O
ð1Þ
O
L
L
L
2
3
1a
L = PPh3
We now wish to report new acyl-alkynyl-iridium
from reactions of alkyl-carbonyl-iridium (1) with
RC„CH and cis-bis(alkynyl)-iridacycles containing vi-
nyl acetate (–C(@CHR)-OC(CH3)O–) ligand via 1,1-
insertion of RC„CH into Ir–O bond of g2-carboxylato
iridium complexes.
*
Corresponding authors. Tel.: +82 2 705 8448; fax: +82 2 701 0967
(C.S. Chin), Tel.: +82 2 714 5915 (H. Lee).
E-mail addresses: cschin@sogang.ac.kr (C.S. Chin), hleegood@
sogang.ac.kr (H. Lee).
0022-328X/$ - see front matter ꢀ 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.11.040

C.S. Chin et al. / Journal of Organometallic Chemistry 690 (2005) 1306–1313
1307
2. Results and discussion
Unlike those reactions of HC„CH in Eq. (1), reac-
tions of 1 with substituted alkynes (RC„CH: R = Ph,
p-C6H4CH3) give neither the insertion products (ana-
logue of 2) nor the carbene complexes (analogue of 3)
but a mixture of uncharacterized complexes. In the pres-
ence of NEt3, however, acyl-alkynyl-iridium complexes
(4) are obtained in high yields from reactions of 1 with
RC„CH (Eq. (2)). Formation of acyl-alkynyl iridium
complexes 4 may be understood by the similar reaction
pathway suggested for the formation of acyl-alkoxycar-
bene iridium complexes 3 [4] obtained from the reactions
of 1a with HC„CH in the presence of ROH (R = CH3,
CH2CH3) (Eq. (1)).
P2
C3
C2
O2
C1
Ir
C11
C54
C10
O1
C55
O3
P1
Fig. 1. ORTEP drawing of Ir(g2-O2CC6H4CH3)(C„CC6H4CH3)-
(C(@O)CH3)(PPh3)2 (4f) with 50% thermal ellipsoids probability.
+
L
Ir
L
L
R
R
R
HC CR, NEt3
-H+NEt3
OC
H3C
O
O
O
O
HC CR
OC
Ir
R'
R'
Ir
H3C
˚
Selected bond distances (A): Ir–P1 = 2.3410(8); Ir–P2 = 2.3428(8); Ir–
-R'CO2H
H3C
O
L
1
L
4
C1 = 1.977(3), Ir–C54 = 1.996(3), Ir–O1 = 2.124(2); Ir–O2 = 2.526,
L
5
O1–C10 = 1.273(4), O2–C10 = 1.266(4), O3–C54
=
C2 = 1.213(5), C2–C3 = 1.441(5), C10–C11 = 1.488(5). Selected bond
1.204(4), C1–
R = Ph, R' = CH3 (a)
R = p-C6H4CH3,R ' = CH3 (b)
R = R' = Ph (c)
R = p-C6H4CH3,R ' = Ph (d)
R = Ph, R' = p-C6H4CH3 (e)
R = R' = p-C6H4CH3 (f)
L =PPh3
R' = CH3 (a)
=Ph (b)
R = Ph (a), p-tolyl (b)
angles (ꢁ): C1–Ir–C54 = 94.77(14); C54–Ir–O1 = 94.32(12), C1–
Ir–P1 = 89.47(9),
C54–Ir–P1 = 93.13(10),
O1–Ir–P1 =
90.64(6),
= p-C6H4CH3 (c)
O2–Ir–P1 = 88.20(6), C1–Ir–P1 = 86.18(9), C54–Ir–P2 = 92.04(10),
O1–Ir–P2 = 92.89(6), O2–Ir–P2 = 89.31(6), C10–O1–Ir = 101.65(19),
ð2Þ
C
10–O2–Ir = 115.38(19), O2–C10–O1 = 119.6(3).
Insertion of RC„CH into the Ir–O bond of 1 has
never been detected while the methyl group migration
to the CO ligand (1 ! 4) seems to readily occur as seen
from reactions of 1 with HC„CH in the presence of
alcohol (1a ! 3 in Eq. (1)). The crystal structure of com-
It may be mentioned that the CH3 ligand migration
to the CO ligand has never been observed for related
complexes, [(OH2)(OA)Ir(CH3)(CO)(PPh3)2]+ contain-
ing the two labile O-ligands (OH2 and OA (OClOꢀ3 ,
OTfꢀ)) that are cis to each other and trans to CH3
and CO, respectively [6].
˚
plex 4f (Fig. 1) shows Ir–O2 (2.526 A) being much longer
˚
than Ir–O1 (2.142 A) distance implying the lability of the
Ir–O2 (trans to the acyl ligand) bond in 4. Complexes 4
further react with another RC„CH to give up the g2-
carboxylato ligands and take two alkynyl groups instead
to give cis-bis(alkynyl) complexes 5 [5] (Eq. (2)).
Both the CH3 ligand migration to the CO ligand
(1 ! 4) and the retro-migration of the CH3 group of
the acyl ligand to the metal (4 ! 5) are possible proba-
bly due to the facile rearrangement of the carboxylato
ligands from g2- to g1-bonding mode to provide an ex-
tra coordination site for incoming alkyne. Accordingly,
g1-carboxylato complexes A and B are suggested as the
intermediates for the formation of 4 and 5, respectively
(Eq. (3)).
In order to see the insertion of substituted alkynes
into the Ir–O bond, another types of g2-acetato iridium
complexes 6 and 7 have been investigated. Both com-
plexes 6 and 7 have two Ir–C r-bonds cis to each other
and trans to the g2-O2CCH3 ligand as do the complexes
1 that readily undergo the insertion reaction of the un-
substituted alkyne (HC„CH) into the Ir–O bond (Eq.
(1)). Complexes 6 and 7 readily undergo the 1,1-inser-
tion reaction of substituted alkynes (RC„CH) into
the Ir–O bond to produce iridacycles (8) containing
g2-vinyl acetate (–C(@CHR)–OC–(CH3)O–) ligands
(Eq. (4)). Such 1,1-insertion of substituted terminal
alkynes (HC„CPh, HC„CCO2Me) into the M–O
bond between the metal and g2-carboxylato ligands
has been previously reported for ruthenium [7] and os-
mium [7b] complexes to produce new M–C(@CHR)–
O– units.
L
R
O
HC CR, NEt3
-H+NEt3
OC
H3C
HC CR
1
Ir
4
O
R'
L
A
R
R
L
L
Ir
ð3Þ
R
R
L
L
L
R
R
5
Ir
O
3 RC CH
H3C
O
3 RC CH
H3C
O
O
O
O
O
O
O
-R'CO2H
Ir
Ir
Ir
- CH2=CHCH=CH2
O
O
O
- 2 CH2=CH2
L
R'
L
R'
ð4Þ
L
7
L
6
L
8
B
R
L = PPh3, R=Ph, p-C6H4CH3,R'= CH3,Ph, p-C6H4CH3
L = PPh3, R = Ph (a), p-C6H4CH3 (b)

1308
C.S. Chin et al. / Journal of Organometallic Chemistry 690 (2005) 1306–1313
Reactions of 6 and 7 with two equivalent alkynes
3. Experimental
(RC„CH), respectively give the same cis-bis(alkynyl)-
g2-acetato complexes (Ir(–C„CR)2(g2-O2CR)(PPh3)2,
9 in Eq. (5)) in high yields while no compound contain-
ing g2-vinyl acetate ligands (–C(@CHR)OC(CH3)O–)
has been observed from reactions of complexes 6 and
7 with one equivalent RC„CH.
3.1. General information
A standard vacuum system and Schlenk type glass-
ware were used in most of the experiments in handling
metal complexes although most of the compounds are
stable enough to be handled in air.
NMR spectra were recorded on a Varian 300 or 500
MHz spectrometer for 1H, 75.4 or 126 MHz for 13C and
81 MHz for 31P. Infrared spectra were obtained on a
Nicolet 205. Elemental analyses were carried out with
a Carlo Erba EA1108 at the Organic Chemistry Re-
search Center, Sogang University.
It is interesting to notice that the g2-carboxylato li-
gands of 1 are replaced by the two alkynyl groups leav-
ing the two Ir–C bonds (Ir–CH3 and Ir–CO) intact (Eq.
(2)) while the g2-carboxylato ligands of 6 and 7 remain
intact in the reactions with RC„CH with the Ir–C
bonds (two Ir–CH@CH2 or Ir-CH=CHCH=CH) being re-
placed by two other Ir–C bonds (Ir–C„CR) (Eq. (3)).
It has been also confirmed that complexes 9 further
react with RC„CH to give complexes 8. It is most likely
that the 1,1-insertion of RC„CH into the Ir–O bond
(Eq. (4)) occurs via the intramolecular C–O bond form-
ing reaction between the oxygen atom of the acetato li-
gand and the a-carbon of the vinylidene ligand of the
intermediate C as shown in Eq. (5). The two alkynyl li-
gands cis to each other in complexes 9 may allow the
insertion of substituted alkynes (RC„CH) into the Ir–
O bond as they occupy smaller space in the immediate
surroundings of the metal than do the two cis ligands,
CH3 and CO, of 1. It may also be said that the two eth-
enyl groups of 6 and 1,3-butadien-1,4-diyl ligand of 7
are less favorable than the cis-bis(alkynyl) ligands in 9
for the insertion of substituted alkynes into the Ir–O
bond due to steric reasons.
3.2. Synthesis and reactions
[Ir(CH3)(CO)(g2-O2CR0)(PPh3)2]OTf (1) were pre-
pared by the literature method [4].
3.2.1. Synthesis of Ir(C„CR)(COCH3)(g2-O2CR0)
(PPh3)2 (4, R = Ph, R0 = CH3 (a), R = p-C6H4CH3,
R0 = CH3 (b), R = R0 = Ph (c), R = p-C6H4CH3,
R0 = Ph (d), R = Ph, R0 = p-C6H4CH3 (e), R = R0 =
p-C6H4CH3 (f))
These complexes were prepared in the same manner
as described below for 4a. The reaction mixture of 1a
(0.11 g, 0.14 mmol) and PhC„CH (0.017 mL, 0.14
mmol) in the presence of NEt3 (0.020 mL, 0.14 mmol)
was stirred at room temperature for 10 min. Addition
of methanol (20 mL) to the CHCl3 solution resulted in
yellow microcrystals of 4a which were collected by filtra-
tion, washed with methanol (3 · 20 mL), and dried
under vacuum. The yield was 0.088 g and 98% based
on of Ir(C(@O)CH3)(–C„CC6H5)(g2-O2CCH3)(PPh3)2
(4a).
L
L
R
R
R
R
O
R'C CH
O
O
Ir
8
Ir
O
C
R'
C
L
9
ð5Þ
L
H
C
L = PPh3
R = R' = C6H5 (a); R = R' =p-C6H4CH3 (b); R = p-C6H4CH3, R' = H (c)
Ir(C(@O)CH3)(–C„CC6H5)(g2-O2CCH3)(PPh3)2 (4a).
1H NMR (500 MHz, CDCl3): d 7.02 (t, metha-protons
of Ir–C„CC6H5, J(H–H) = 7 Hz, 2H), 6.94 (t, para-
proton of Ir–C„CC6H5, J(H–H) = 7 Hz, 1H) and
6.54 (d, Ir–C„CC6H5, ortho-protons, J(HH) = 7.5 Hz,
2H), 1.50 (s, Ir–C(@O)CH3, 3H), 0.56 (s, Ir–g2–
O2CCH3, 3H). 13C NMR (125 MHz, CDCl3): d 191.6
(t, Ir–C@O)CH3, J(CP) = 4 Hz), 182.9 (s, Ir–g2-
O2CCH3), 131.0, 127.5 and 124.3 (both s, CH carbons
of Ir–C„CC6H5), 106.6 (s, Ir–C„CC6H5), 76.0 (t, Ir–
C„CC6H5, J(CP) = 13 Hz), 36.7 (s, Ir–C(@O)CH3),
22.4 (s, Ir–g2-O2CCH3). HETCOR (1H (500
MHz) ! 13C (126 MHz)): d 1.50 ! 36.7; 0.56 ! 22.4.
31P{1H} NMR (81 MHz, CDCl3): d 8.3 (s, Ir–PPh3).
IR (KBr, cmꢀ1): 2113 (s, mC„C), 1634 (s, mC@O). Anal.
Calc. for Ir1P2O3C48H41: C, 62.66; H, 4.49. Found: C,
62.63; H, 4.48.
New iridium complexes (4, 6–9) are unambiguously
identified by detailed spectral and elemental analysis
data and crystal structure determination by X-ray dif-
fraction data analysis for 4f (see Section 3 and Support-
ing Information). Most assignments of spectral signals
measured for 4 and 6–9 are unambiguously straightfor-
ward by comparing numerous data for related com-
pounds previously reported [3,4,7–9].
In summary, we have observed (i) alkyl group migra-
tion to CO ligand to give cis-alkynyl-acyl-iridium
complexes (4) from the reactions of cis-alkyl-carbonyl-
iridium complexes with substituted alkynes, (ii) retro-
migration of CH3 group of the acyl ligands from further
reactions of 4 with alkynes to produce alkyl-carbonyl-
cis-bis(alkynyl) complexes (5) and (iii) 1,1-insertion of
substituted alkynes into the Ir–O bond in g2-acetato-
bis(alkynyl) iridium complexes (9) to produce cis-
bis(alkynyl)iridacycles (8) containing vinyl acetate
ligands.
Ir(C(@O)CH3)(-C„C-p-C6H4CH3)(g2-O2CCH3)(PPh3)2
(4b). 1H NMR (500 MHz, CDCl3): d 6.45–6.85 (AB quar-
tet with Dm/J = 23.2, Ir–C„C-p-C6H4CH3, 4H), 2.24

C.S. Chin et al. / Journal of Organometallic Chemistry 690 (2005) 1306–1313
1309
(s, Ir–C„C-p-C6H4CH3, 3H), 1.49 (s, Ir–C(@O)CH3,
3H), 0.56 (s, Ir–g2-O2CCH3, 3H). 13C NMR (125 MHz,
CDCl3): d 192.0 (t, Ir–C(@O)CH3), 182.6 (s, Ir–g2-
O2CCH3), 130.6 and 128.1 (both s, CH carbons of Ir–
C„CC6H4CH3), 106.2 (s, Ir–C„C-p-C6H4CH3), 73.9
(t, Ir–C„C-p-C6H4CH3, J(CP) = 14 Hz), 36.5 (s, Ir–
COCH3), 22.2 (s, Ir–g2-O2CCH3), 21.1 (s, Ir–C„C-p-
C6H4CH3). HETCOR (1H (500 MHz) ! 13C (126
31P{1H} NMR (81 MHz, CDCl3): d 8.3 (s, Ir–PPh3). IR
(KBr, cmꢀ1): 2114 (s, mC„C), 1634 (s, mC@O). Anal. Calc.
for Ir1P2O3C49H43: C, 63.01; H, 4.64. Found: C, 63.00;
H, 4.62.
Ir(C(@O)CH3)(-C„CC6H5)(g2-O2CC6H5)(PPh3)2 (4c).
1H NMR (500 MHz, CDCl3): 7.08–6.61 (m, Ir–g2-
O2CC6H5 and Ir–C„CC6H5, 10H), 1.42 (s, Ir–
C(@O)CH3, 3H). 13C NMR (125 MHz, CDCl3): 193.4
(t, Ir–C(@O)CH3, J(CP) = 5 Hz), 177.8 (s, Ir–g2-
O2CCH3), 106.2 (s, Ir–C„CC6H5), 75.6 (t, Ir–
C„CC6H5, J(CP) = 14 Hz), 36.9 (s, Ir–C(@O)CH3).
HETCOR (1H (500 MHz) ! 13C (126 MHz)): d
1.42 ! 36.9. 31P{1H} NMR (81 MHz, CDCl3): d 7.4
(s, Ir–PPh3). IR (KBr, cmꢀ1): 2113 (s, mC„C), 1636 (s,
MHz) ! 13C (126 MHz)): d 2.20 ! 21.5; 1.45 ! 36.9.
31P{1H} NMR (81 MHz, CDCl3): d 7.4 (s, Ir–PPh3).
IR (KBr, cmꢀ1): 2111 (s, mC„C), 1637 (s, mC@O). Anal.
Calc. for Ir1P2O3C54H45: C, 65.11; H, 4.55. Found: C,
65.11; H, 4.46.
Ir(C(@O)CH3)(–C„C-p-C6H4CH3)(g2-O2C-p-C6H4-
CH3)(PPh3)2 (4f). 1H NMR (500 MHz, CDCl3): d 6.97–
6.55 (m, Ir–g2-O2C-p-C6H4CH3 and Ir–C„CC6H4CH3,
8H), 2.29 (s, Ir–C„CC6H4CH3, 3H), 2.22 (g2-O2C-p-
C6H4CH3), 1.43 (s, Ir–C(@O)CH3, 3H). 13C NMR
MHz)):
d
2.24 ! 21.1; 1.49 ! 36.5; 0.56 ! 22.2.
(125 MHz, CDCl3):
d 194.0 (t, Ir–C(@O)CH3,
J(CP) = 5 Hz), 178.0 (s, Ir–g2-O2C-p-C6H4CH3),
130.7, 130.3, 128.1, 126.2 (s, CH carbons of Ir–C„C-
p-C6H4CH3 and Ir–g2-O2C-p-C6H4CH3), 105.8 (s, Ir–
C„C-p-C6H4CH3), 73.9 (t, Ir–C„C-p-C6H4CH3,
J(CP) = 13 Hz), 37.0 (s, Ir–C(@O)CH3), 21.5 (g2-O2C-
p-C6H4CH3), 21.3 (s, Ir–C„C-p-C6H4CH3). HETCOR
(1H (500 MHz) ! 13C (126 MHz)): d 2.29 ! 21.3;
2.22 ! 21.5; 1.43 ! 37.0. 31P{1H} NMR (81 MHz,
CDCl3): d 7.4 (s, Ir–PPh3). IR (KBr, cmꢀ1): 2112 (s,
mC„C), 1637 (s, mC@O). Anal. Calc. for Ir1P2O3C55H47:
C, 65.40; H, 4.69. Found: C, 65.36; H, 4.66.
m
C@O). Anal. Calc. for Ir1P2O3C53H43: C, 64.82; H,
4.41. Found: C, 64.79; H, 4.40.
3.2.2. Synthesis of Ir(CH3)(CO)(–C„CR)2(PPh3)2
(5, R = Ph (a), p-C6H4CH3 (b))
Ir(C(@O)CH3)(–C„C-p-C6H4CH3)(g2-O2CC6H5)-
These complexes were prepared in the same manner
as described below for 5b. The reaction mixture of 4b
(0.11 g, 0.14 mmol) and p-tolyl-C„CH (0.015 g, 0.15
mmol) was stirred at room temperature for 30 min. Ace-
tic acid was removed with water by extraction (2 · 10
mL) and addition of methanol (20 mL) to the CHCl3
solution resulted in yellow microcrystals of 5b which
were collected by filtration, washed with methanol
(3 · 20 mL), and dried under vacuum. The yield was
0.11 g and 98% based on of Ir(CH3)(CO)(C„C-p-
1
(PPh3)2 (4d). H NMR (500 MHz, CDCl3): d 7.10 (t,
para-proton of Ir–g2-O2CC6H5, para, J(HH) = 7 Hz,
1H), 7.06 (d, ortho-protons of Ir–g2-O2CC6H5,
J(HH) = 7.5 Hz, 2H) and 6.93 (t, metha-protons of Ir-
g2-O2CC6H5, J(HH) = 7.5 Hz, 2H), 6.56–6.86 (AB
quartet with m/J = 19.6, Ir–C„C-p-C6H4CH3, 4H),
2.27 (s, Ir–C„C-p-C6H4CH3, 3H), 1.43 (s, Ir–
C(@O)CH3, 3H). 13C NMR (125 MHz, CDCl3): d
193.3 (t, Ir–C(@O)CH3), 177.6 (s, Ir–g2-O2CC6H5),
130.7 and 128.1 (s, CH carbons of Ir–C„C-p-
C6H4CH3), 130.3, 128.1 and 126.2 (s, CH carbons of
Ir–C„CC6H5), 105.7 (s, Ir–C„C-p-C6H4CH3), 73.4
(t, Ir–C„C-p-C6H4CH3), 36.7 (s, Ir–COCH3), 21.1
(s, Ir–C„C-p-C6H4CH3). HETCOR (1H (500
MHz) ! 13C (126 MHz)): d 2.27 ! 21.1; 1.43 ! 36.7.
31P{1H} NMR (81 MHz, CDCl3): d 7.5 (s, Ir–PPh3).
IR (KBr, cmꢀ1): 2112 (s, mC„C), 1637 (s, mC@O). Anal.
Calc. for Ir1P2O3C54H45: C, 65.11; H, 4.55. Found: C,
65.20; H, 4.49.
1
C6H4CH3)2(PPh3)2 (5b) [3c] which was identified by H
NMR and IR spectral measurement.
3.2.3. Preparation of Ir(CH@CH2)2(g2-O2CCH3)-
(PPh3)2 (6)
A 0.1 g (0.1 mmol) of [Ir(CH@CH2)2(NCCH3)2-
(PPh3)2]OTf [3d] in CHCl3 (10 mL) was stirred in the
presence of CH3CO2Na (0.15 mmol) at 25 oC for 3 h be-
fore MeOH (30 mL) was added to precipitate beige mi-
cro-crystals which were collected by filtration, washed
with n-pentane (3 · 10 mL) and dried under vacuum.
Ir(C(@O)CH3)(–C„CC6H5)(g2-O2C-p-C6H4CH3)-
1
(PPh3)2 (4e). H NMR (500 MHz, CDCl3): d 7.07 (t,
The yield was 0.08
g
and 98% based on
metha-protons of Ir–C„CC6H5, J(HH) = 7 Hz, 2H)
and 6.98 (d, ortho-proton of Ir–CCC6H5, J(HH) = 7.5
Hz, 2H), 6.64–6.74 (AB quartet with Dm/J = 4.3, Ir–g2-
O2C-p-C6H4CH3, 4H), 2.20 (g2-O2C-p-C6H4CH3), 1.45
(s, Ir–C(@O)CH3, 3H). 13C NMR (125 MHz, CDCl3):
d 193.4 (t, Ir–C(@O)CH3, J(CP) = 5 Hz), 177.8 (s, Ir–
g2-O2C-p-C6H4CH3), 106.2 (s, Ir–C„CC6H5), 75.6 (t,
Ir–C„CC6H5, J(CP) = 14 Hz), 36.9 (s, Ir–C(@O)CH3),
21.5 (s, g2-O2C-p-C6H4CH3). HETCOR (1H (500
Ir(CH@CH2)2(g2-O2CCH3)(PPh3)2 (6). 1H NMR
(CDCl3, 300 MHz): d 7.36–7.50 (m, P(C6H5)3, 30H),
7.22 (m, Ir–CH@CH2, 2H), 4.94 (d, Ir–CH@CHtransHcis,
J(HH) = 9.3 Hz, 2H), 4.88 (d, Ir–CH@CHtransHcis,
J(HH) = 16.8 Hz, 2H), 0.91 (s, Ir–g2-O2CCH3, 3H).
13C NMR (CDCl3, 75.4 MHz): d 183.2 (s, Ir–g2-
O2CCH3), 124.7 (t, J(CP) = 9.5 Hz, Ir–CH@CH2),
116.0 (br s, Ir–CH@CH2), 24.0 (s, Ir–g2-O2CCH3),
135.0, 130.2, 130.0 and 127.9 (P(C6H5)3). 31P{1H}

1310
C.S. Chin et al. / Journal of Organometallic Chemistry 690 (2005) 1306–1313
NMR (CDCl3, 81 MHz): d 8.37 (s, PPh3). IR (KBr,
cmꢀ1): 1553 (m, mC@O), 1529 (m, mC@C). Anal. Cald for
Ir1P2O2C42H39: C, 60.78; H, 4.74. Found: C, 60.76; H,
4.71.
100.8 (t, J(CP) = 2.5 Hz) (Ir–C„CPh), 98.5 (t,
J(CP) = 14.6 Hz) and 68.8 (t, J(CP) = 14.2 Hz) (Ir–
Ir-C(=CHPh)OC(CH )=O
C„CPh), 16.9 (s,
), 135.3,
3
130.5, 130.2 and 127.6 (P(C6H5)). HETCOR (1H (500
MHz) ! 13C (126 MHz)): d 1.44 ! 16.9; 4.98 ! 121.4.
31P{1H} NMR (CDCl3, 81 MHz): d ꢀ0.79 (s, PPh3).
IR (KBr, cmꢀ1): 2127 and 2111 (s, mC„C), 1631 (s,
3.2.4. Preparation of
(PPh3)2 (7)
(g2-O CCH )-
Ir(CH=CHCH=CH)
2
3
[Ir(CH=CHCH=CH)
To
a
solution of
(NCCH3)-
mC@O), 1604 (s, mC@C). Anal. Calc. for Ir1P2O2C62H49:
C, 68.94; H, 4.57. Found: C, 68.91; H, 4.54.
Ir(–C(@CH-p-C6H4CH3)OC(CH3)@O)(–C„C-
p-C6H4CH3)2(PPh3)2 (8b). 1H NMR (CDCl3, 500
(CO)(PPh3)2]OTF [9] (0.1 g, 0.1 mmol) in CHCl3 (10
mL) were Me3NO (0.019 g, 0.25 mmol) and CH3CN
(0.012 g, 0.3 mmol) added and the reaction mixture
was stirred at 25 ꢁC under N2 for 30 min before the pale
yellow solution turned light brown. Excess Me3NO and
NMe3 were removed by extraction with H2O (2 · 10
mL). A light brown solution of CHCl3 was stirred in
the presence of CH3CO2Na (0.15 mmol) at 25 ꢁC for 3
h before MeOH (30 mL) was added to precipitate beige
micro-crystals which were collected by filtration, washed
with n-pentane (3 · 10 mL) and dried under vacuum.
MHz):
7.01 (m, Ir–C„C-p-C6H4CH3, 12H), 4.97 (br s,
Ir-C(=CH-p-C H CH )OC(CH )=O
d
7.26–7.95 (m, P(C6H5)3, 30H), 6.29–
), 2.35, 2.31 and 2.26
Ir-C(=CH-p-C H CH )OC(CH )=O
6
4
3
3
(s,
H4CH3, 9H), 1.40 (s,
3H). 13C NMR (125 MHz, CDCl3): d 180.9 (s,
Ir-C(=CH- p-C H CH )OC(CH )=O
and Ir–C„C-p-C6-
6
4
3
3
Ir-C(=CH-p-C H CH )OC(CH )=O
,
6
4
3
3
), 171.1 (t, J(CP) =
Ir-C(=CH-p-C H CH )OC(CH )=O
6
4
3
3
10.7 Hz,
), 131.0,
6
4
3
3
The yield was 0.097
g
and 98% based on
130.9, 128.5, 128.4, 128.3, and 128.1 (CH carbons of
p-C6H4CH3), 135.2, 135.1, 133.9, 133.6, 133.5 and
127.2 (Cipso of C6H4CH3), 121.4 (t, J(CP) = 2.5 Hz,
Ir(CH=CHCH=CH)(g2-O2CCH3)(PPh3)2 (7). 1H NMR
(CDCl3, 500 MHz): d 7.3–7.5 (m, P(C6H5)3, 30H), 6.86
Ir-CH=CHCH=CH
Ir-CH=CHCH=CH
,
(m,
, 2H), 5.63 (m,
), 114.5 (s) and 100.4
Ir-C(=CH-p-C6H4CH3)OC(CH3)=O
2H), 0.48 (s, Ir–g2-O2- CCH3, 3H). 13C NMR (CDCl3,
(t, J(CP) = 2.3 Hz) (Ir–C„C-p-C6H4CH3), 97.2 (t,
J(CP) = 14.6 Hz) and 67.0 (t, J(CP) = 14.1 Hz) (Ir–
C„C-p-C6H4CH3), 21.44 and 21.40 (both s, Ir–C„C-
126 MHz): d 183.5 (s, Ir–g2-O2CCH3), 143.6 (s,
Ir-CH=CHCH=CH),
132.9
(t,
J(C-P) = 8.0
Hz,
2
Ir-CH=CHCH=CH
Ir-C(=CH-p-C H CH )OC(CH )=O
), 24.1 (s, Ir–g -O2CCH3), 135.05,
p-C6H4CH3
and
,
6
4
3
3
129.81, 129.79 and 127.48 (P(C6H5)3). HETCOR (1H
16.8
Ir-C(=CH-p-C6H4CH3)OC(CH3)=O, 135.4, 130.2,
(500 MHz) ! 13C (126 MHz)):
d
0.48 ! 24.1;
129.8, and 127.6 (P(C6H5)3). HETCOR (1H (500
MHz) ! 13C (126 MHz)): d 1.40 ! 16.8; 2.35 and
2.31 ! 21.44; 2.26 ! 21.40; 4.97 ! 121.4. 31P{1H}
NMR (CDCl3, 81 MHz): d ꢀ1.00 (s, PPh3). IR (KBr,
cmꢀ1): 2123 and 2109 (s, mC„C), 1636 (s, mC@O), 1593
(s, mC@C). Anal. Calc. for Ir1P2O2C65H55: C, 69.56; H,
4.94. Found: C, 69.51; H, 4.90.
5.63 ! 143.6; 6.86 ! 132.9. 31P{1H} NMR (CDCl3, 81
MHz): d 13.36 (s, PPh3). Anal. Calc. for Ir1P2O2C42H37:
C, 60.93; H, 4.50. Found: C, 60.90; H, 4.49.
3.2.5. Reactions of complexes 6 and 7 with excess
Ir(-C(=CHR)OC(CH )=O)
RC„CH: formation of
(–C„CR)2(PPh3)2 (8)
-
3
Compounds 8 were prepared by the same method as
described below for 8a. A CHCl3 (10 mL) solution of 6
(or 7) (0.10 g, 0.1 mmol) and C6H5C„CH (0.033 g, 0.33
mmol) was stirred at 25 ꢁC for 10 min before n-pentane
(20 mL) was added to precipitate light yellow micro-
crystals which were collected by filtration, washed with
n-pentane (3 · 10 mL) and dried under vacuum. The
3.2.6. Reactions of Ir(–CH@CH2)2(g2-O2CCH3)-
(PPh3)2 (6) with two equivalent RC„CH: Formation of
Ir(–C„CR)2(g2-O2CCH3)(PPh3)2 (9, R = Ph (a),
p-tolyl (b), cyclohex-1-enyl (c)) and ethylene
(CH2@CH2)
These compounds were prepared by the same method
as described below for 9a. A CHCl3 (10 mL) solution of
6 (0.10 g, 0.1 mmol) and C6H5C„CH (0.020 g, 0.20
mmol) was stirred at 25 ꢁC for 10 min before n-pentane
(20 mL) was added to precipitate light yellow micro-
crystals which were collected by filtration, washed with
n-pentane (3 · 10 mL) and dried under vacuum. The
yield was 0.11 g and 98% based on Ir(–C„C–
C6H5)2(g2-O2CCH3)(PPh3)2 (9a).
yield
was
0.11
g
and
98%
based
on
Ir(-C(=CHPh)OC(CH )=O)
(–C „ CPh)2(PPh3)2 (8a).
3
Ir(-C(=CHPh)OC(CH )=O)
(–C „ C–C6H5)2(PPh3)2 (8a).
3
1H NMR (CDCl3, 500 MHz):
d
7.26–7.94 (m,
P(C6H5)3, 30H), 6.40–7.20 (m, Ir–C„C–C6H5,
15H), 4.98 (br s,
Ir-C(=CHPh)OC(CH )=O)
, 1.44 (s,
3
, 3H). 13C NMR (125 MHz,
Ir-C(=CHPh)OC(CH )=O)
3
1
CDCl3): d 181.1 (s,
J(CP) = 10.4 Hz,
, 172.3 (t,
, 137.7 and
Ir(–C„CC6H5)2(g2-O2CCH3)(PPh3)2 (9a). H NMR
Ir-C(=CHPh)OC(CH )=O)
3
Ir-C(=CHPh)OC(CH )=O)
(CDCl3, 500 MHz): d 7.18–7.77 (m, P(C6H5)3, 30H),
6.84–6.93 (m, metha- and para-protons of C„CC6H5,
6H), 6.14 (d, ortho-protons of C„CC6H5, 4H), 0.62
(s, Ir–g2-O2CCH3, 3H). 13C NMR (CDCl3, 126 MHz):
d 188.1 (s, Ir–g2-O2CCH3), 131.3, 126.9 and 124.2 (s,
3
130.0 (Cipso carbons of C6H5), 131.2, 131.1, 129.9,
129.8, 128.5, 127.4, 126.3, 124.6, 124.2, and 124.0 (CH
carbons of C6H5), 121.4 (t, J(CP) = 3.1 Hz,
Ir-C(=CHPh)OC(CH )=O)
, 114.8 (t, J(CP) = 1.9 Hz) and
3

C.S. Chin et al. / Journal of Organometallic Chemistry 690 (2005) 1306–1313
1311
CH carbons of Ir–C„CC6H5), 128.8 (s, ipso-carbons of
Ir–C„CC6H5), 103.9 (s, Ir–C„C), 60.8 (t, J(C–
P) = 13.0 Hz, Ir–C„C), 23.3 (s, Ir–g2-O2CCH3),
135.2, 130.2, 130.0 and 127.9 (P(C6H5)3). HETCOR
(1H (500 MHz) ! 13C (126 MHz)): d 6.91 ! 126.9;
6.86 ! 124.2; 6.14 ! 131.3; 0.62 ! 23.3. 31P{1H}
NMR (81 MHz, CDCl3): d 10.43 (s, PPh3). IR (KBr,
cmꢀ1): 2118.4 (s, C„C). Anal. Calc. for Ir1P2O2C54H43:
C, 66.31; H, 4.43. Found: C, 66.25; H, 4.38.
Ir-C(=CH2)-OC(CH3)=O), 130.4, 130.3, 127.9 and 127.6
(s, CH carbons of Ir–C„C-p-C6H4CH3), 133.0,
132.9.5, 131.9 and 131.8 (s, Cipso of Ir–C„C-p-
C6H4CH3), 134.8, 130.3, 129.3 and 127.1. (P(C6H5)3).
31P{1H} NMR (81 MHz, CDCl3): d ꢀ3.33 (s, PPh3).
IR (KBr, cmꢀ1): 2122.3 and 2107.8 (s, mC„C). Anal.
Calc. for Ir1P2O2C58H49: C, 67.49; H, 4.78. Found: C,
67.47; H, 4.79.
Ir(–C„C-p-C6H4CH3)2(g2-O2CCH3)(PPh3)2 (9b). 1H
NMR (CDCl3, 500 MHz): d 7.20–7.77 (m, P(C6H5)3,
30H), 6.04–6.74 (AB quartet, Ir–C„C–C6H4CH3, Dv/
J = 42.7, J(HA–HB) = 8.0 Hz, 8H), 2.21 (s, C6H4CH3,
6H), 0.62 (s, Ir–g2-O2CCH3, 3H). 13C NMR (CDCl3,
126 MHz): d 188.0 (s, Ir–g2-O2CCH3), 133.7 and 129.5
(both s, Cipso of Ir–C„C-p-C6H4CH3), 131.1 and
127.7 (both s, CH carbons of Ir–C„C-p-C6H4CH3),
103.6 (s, Ir–C„C-p-C6H4CH3), 58.9 (t, J(C–P) = 10.1
Hz, Ir–C„C-p-C6H4CH3), 23.3 (s, Ir–g2-O2CCH3),
21.0 (s, Ir–C„C-p-C6H4CH3), 135.2, 130.1, 129.1 and
127.8. (P(C6H5)3). HETCOR (1H (500 MHz) ! 13C
(126 MHz)): d 6.73 ! 127.7; 6.05 ! 131.1; 2.21 ! 21.0;
0.62 ! 23.3. 31P{1H} NMR (81 MHz, CDCl3): d 10.43
(s, PPh3). IR (KBr, cmꢀ1): 2119.8 (s, mC„C). Anal. Calc.
for Ir1P2O2C56H47: C, 66.85; H, 4.71. Found: C, 66.88;
3.3. X-ray structure determination of Ir(C(@O)CH3)-
(–CC-p-C6H4CH3)(g2-O2C-p-C6H4CH3)(PPh3)2 (4f)
Crystals of 4f were grown by slow evaporation from
CHCl3 solution. Preliminary examination and data col-
lection were performed using a Bruker SMART CCD
Detector single crystal X-Ray diffractometer using
a
graphite monochromated Mo Ka radiation
˚
(k = 0.71073 A) source equipped with a sealed tube
X-ray source at ꢀ100 ꢁC for 4f. Preliminary unit cell
Table 1
Details of crystallographic data collection for 4f
4f
H, 4.76.
Chemical formula
Chemical formula weight
Temperature (K)
Crystal dimension (mm)
Crystal system
C55H47IrO3P2
1010.14
2
Ir(-C≡C-C=CH(CH ) CH )
(g -O CCH (PPh )
(9c).
2 3
2
2
3
3 2
1H NMR (CDCl3, 200 MHz):
d 7.11–7.86 (m,
173(2)
0.30 · 0.28 · 0.10
Triclinic
P(C6H5)3, 30H), 4.56 (s, Ir-C≡C-C=CH(CH2)3CH2, 2H),
0.54 (s, Ir–g2-O2CCH3, 3H) 1.14–1.90 (m,
Ir-C≡C-C=CH(CH2)3CH2, 16H). 31P{1H} NMR (81
MHz, CDCl3): d 9.82 (s, PPh3). Anal. Calc. for Ir1-
P2O2C54H51: C, 65.77; H, 5.21. Found: C, 65.79; H,
5.28.
ꢀ
Space group
Color of crystal
P1
Yellow
Unit cell dimensions
˚
a (A)
˚
9.9059(7)
11.9810(9)
20.9544(16)
94.4990(10)
90.6670(10)
98.2910(10)
2452.7(3)
2
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
3.2.7. Reactions of Ir(–C„Cp-tolyl)2(g2-O2CCH3)-
(PPh3)2 (9b) with HC„CH: formation of
3
˚
Ir(O=C(CH )-O-C=CH )
(–C„C-p-tolyl) (PPh ) (8c)
3
2
V (A )
2
3 2
Z
A 0.1 g (0.1 mmol) of 9b in CHCl3 (10 mL) was stir-
red under HC„CH (1 atm) at 25 ꢁC. Within 30 min,
beige micro-crystals were precipitated and were collected
by filtration, washed with n-pentane (3 · 10 mL) and
dried under vacuum. The yield was 0.11 g and 98%
q(calc) (g cmꢀ1
)
1.529
2.995
1132
l (mmꢀ1
F(000)
)
Radiation
Wavelength
h Range (ꢁ)
hkl Range
Mo Ka
0.71069
1.72–28.28
ꢀ11 6 h 6 13
ꢀ15 6 k 6 7
ꢀ26 6 l 6 27
15301
Ir(C(=CH )-OC(CH )=O)
(–C„C-C6H4CH3)2-
based on
2
3
1
(PPh3)2 (8c). H NMR (CDCl3, 500 MHz): d 7.30–8.10
(m, P(C6H5)3, 30H), 6.26–6.92 (m, Ir–C„C–C6H4CH3,
8H), 5.02 (d, J(HH) = 1.5 Hz) and 4.18 (d,
J(HH) = 1.5 Hz) (
and 2.24 (s,
Ir-C(=CH )-OC(CH )=O
MHz): 180.1 (s,
(t, J(CP) = 10.6 Hz,
No. of reflections
No. of unique data
No. of observed (jFoj > rFo) data
No. of parameters
Scan type
Ir-C(=CH )-O-C(CH )=O
, 2H), 2.29
1.15 (s,
2
3
11015
9861
589
C6H4CH3,
, 3H). 13C NMR (CDCl3, 126
Ir-C(=CH )-OC(CH )=O
Ir-C(=CH )-OC(CH )=O
6H),
2
3
p and x scan
0.0355
0.0759
d
), 175.0
), 113.0
2
3
R1
2
3
wR2
and 101.4 (s, Ir–C„C-p-C6H4CH3), 107.7 (s,
Ir-C(=CH )-OC(CH )=O
and 65.2 (t, J(CP) = 14.3 Hz) (Ir–C„C-p-C6H4-
CH3), 20.9 (s, Ir–C„C-p-C6H4CH3), 15.7 (s,
Goodness-of-fit
P
1.048
P
P
), 96.1 (t, J(CP) = 15.0 Hz)
2
2 0:5
2
3
R1 = [ jFoj ꢀ jFcj/jFoj], wR2 ¼ ½ wðF 2o ꢀ F c2Þ = wðF o2Þ ꢁ
.
weighting_scheme
2
w ¼ 1=½r2ðF o2Þ þ ð0:0388PÞ þ 1:8667Pꢁ; where P ¼ ðF o2 þ 2F 2c Þ=3.

1312
C.S. Chin et al. / Journal of Organometallic Chemistry 690 (2005) 1306–1313
constants were determined with a set of 45 narrow
frames (0.3 in x) scans. A data set collected consists of
1286 frames of intensity data collected with a frame
width of 0.3 in x and counting time of 10 s/frame at a
crystal to detector distance of 5.0 cm. The double pass
method of scanning was used to exclude any noise.
The collected frames were integrated using an orienta-
tion matrix determined from the narrow frame scans.
SMART and SAINT software packages (Bruker Analytical
X-ray, Madison, WI, 1997) were used for data collection
and data integration. Analysis of the integrated data did
not show any decay. Final cell constants were deter-
mined by a global refinement of 5225 reflections
(2.3 < h < 28.2). Collected data were corrected for
absorbance using SADABS based upon the Laue symme-
try using equivalent reflections. Crystal data and inten-
sity data collection parameters are listed in Table 1.
Structure solution and refinement of the structure were
carried out using the SHELXTL-PLUS (5.03) software
package (Sheldrick, G.M., Siemens Analytical X-Ray
Division, Madison, WI, 1997). The structure was solved
by direct method and refined successfully in the space
group P-1. Full-matrix least-squares refinement was car-
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(d) C.S. Chin, H. Lee, H. Park, M. Kim, Organometallics 21
(2002) 3889;
(e) C.S. Chin, M. Kim, H. Lee, S. Noh, K.M. Ok, Organometallics
21 (2002) 4785;
(f) C.S. Chin, G. Won, D. Chong, M. Kim, H. Lee, Acc. Chem.
Res. 35 (2002) 218;
Appendix A. Supplementary material
(g) C.S. Chin, M. Kim, G. Won, H. Chong, H. Lee, Dalton Trans.
(2003) 2325;
Crystallopraphic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Center, CCDC No. 237800. Copies of this infor-
mation can be obtained free of charge via www.ccdc.ca-
m.ac.uk/conts/retrieving.html (or from the Cambridge
Crystallograhpic Data Centre, 12, Union Road, Cam-
bridge CB2 1EZ, UK; fax: +44 1223 336033; e-mail: de-
posit@ccdc.cam.ac.uk) and 1H, 13C NMR and
HETCOR (1H–13C) spectra data of complexes 4f, 6, 7,
8a, 8c and 9a have been provided as PDF file. Supple-
mentary data associated with this article can be found,
in the online version, at doi:10.1016/j.jorganchem.
2004.11.040.
(h) C.S. Chin, W. Maeng, D. Chong, G. Won, B. Lee, Y.J. Park,
J.M. Shin, Organometallics 18 (1999) 2210.
[4] C.S. Chin, M. Kim, M.K. Lee, H. Lee, Organometallics 22 (2003)
3239.
[5] cis-Bis (alkynyl) iridium complexes Ir(C„CR)2(CH3)(CO)(PPh3)2
(5) have been also synthesized by other method in our laboratory
(see [3c]).
[6] Unpublished results. [(OH2)(OClO3)Ir(CH3)(CO)(PPh3)2]+ was
previously reported C.S. Chin, M. Lee, M. Oh, G. Won, Y.J.
Park, M. Kim. Organometallics 19 (2000) 1572, and [(OH2)(OT-
f)Ir(CH3)(CO)(PPh3)2]+ is readily prepared by replacing OClO3ꢀ
with OTfꢀ.
[7] (a) M.S. Sanford, M.R. Valdez, R.H. Grubbs, Organometallics 20
(2001) 5455;

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[8] (a) I. Ara, J.R. Berenguer, E. Eguizabal, J. Fornies, E. Lalinde, F.
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