Coordination of aniline to an (η1allenyl)iridium complex leading to hydroanilination

Article abstract of DOI:10.1021/om9602623

Formation of the N-arylated η³-aza-TMM complexes of iridium from regioselective hydroanilination of an octahedral (η¹-allenyl)iridium complex has been studied. (OC-6-42)-Ir(Cl)(PPh₃)₂(OTf)(CO)(η ¹-CHC

Full text of DOI:10.1021/om9602623

1476
Organometallics 1997, 16, 1476-1483
Coor d in a tion of An ilin e to a n (η1-Allen yl)ir id iu m
Com p lex Lea d in g to Hyd r oa n ilin a tion †
J wu-Ting Chen,* Yu-Kun Chen, J iane-Bond Chu, Gene-Hsiang Lee, and
Yu Wang
Department of Chemistry, National Taiwan University, Taipei, Taiwan 106, Republic of China
Received April 3, 1996X
Formation of the N-arylated η3-aza-TMM complexes of iridium from regioselective
hydroanilination of an octahedral (η1-allenyl)iridium complex has been studied. (OC-6-42)-
Ir(Cl)(PPh3)2(OTf)(CO)(η1-CHCCH2) (2) undergoes the substitution of L (L ) NH3, NH2NH2,
MeNH2, EtNH2, iPrNH2, PhCH2NH2) for the triflate ligand to yield {(OC-6-42)-Ir(Cl)(PPh3)2-
(L)(CO)(η1-CHCCH2)}(OTf) (3d -i). In contrast, the reactions of 2 with XC6H4NH2 (X ) F,
NO2, MeO, H, Me), Ph2NH, and Ph(Me)NH result in regioselective addition at the allenyl
ligand, thereby generating the N-arylated η3-aza-TMM complexes 5a -g. The mechanistic
studies confirm that the hydroanilination is preceded by the formation of an aniline-ligated
intermediate.
In tr od u ction
or to the cationic η3-propargyl/allenyl complex [Pt-
(PPh3)2(η3-C3H3)](BF4) led to the formation of the central-
carbon-substituted η3-allyl or N-protonated or alkylated
η3-aza-TMM5 complexes {Pt(PPh3)2[η3-CH2C(Nu)CH2]}-
(X) (Nu ) OH, OR, SR, SeR, NRR′; X ) halide, OTf,
BF4).2b,6 However, the octahedral neutral (η1-allenyl)-
haloiridium complexes Ir(X)(X′)(PPh3)2(CO)(η1-CHCCH2)
(1; X, X′ ) halide) are inert to nucleophilic addition. We
have thus prepared the labile (η1-allenyl)(triflato)-
iridium species (OC-6-42)-Ir(Cl)(PPh3)2(OTf)(CO)(η1-
CHCCH2) (2),7 which can react with water and alcohol
to result in regioselective hydroxylation and alkoxyla-
tion. The iridium complexes with the central-carbon-
substituted η3-allyl ligand are thereby generated.8
To our surprise, the reaction of 2 with ammonia leads
to a product of substitution, {(OC-6-42)-Ir(Cl)(PPh3)2-
(NH3)(CO)(η1-CHCCH2)}(OTf). The expected product of
hydroamination is never observed in such a reaction.
Our successive studies show that complex 2 can react
with aniline and its relatives to produce the N-arylated
η3-aza-TMM complexes. Such distinct reactivities have
spurred us to further investigate the reactions of 2 with
various amine and aniline derivatives as well as the
reaction mechanism. The mechanistic studies confirm
that the hydroanilination is preceded by the formation
of an aniline-ligated intermediate.
Organometallic transformations of transition-metal
allenyl species are useful in organic synthesis.1 Recent
development of metal allenyl chemistry allows for
adding a vast variety of nucleophiles to the allenyl
moiety.2 The involvement of metal in the addition
reactions may contribute to at least two aspects. First,
the bonding between the metal and the allenyl ligand
profoundly affects the chemical reactivity.3 Second, the
coordination of the nucleophile provides the metal with
the opportunity of applying chemical selectivity.4
We previously discovered that adding nucleophiles
such as water, alcohol, thiol, selenol, ammonia, amine,
etc. either to the four-coordinate neutral η1-allenyl
complexes trans-Pt(X)(PPh3)2(η1-CHCCH2) (X ) halide)
† Based on the M.S. thesis of Y.-K.C., National Taiwan University,
1995.
X Abstract published in Advance ACS Abstracts, March 1, 1997.
(1) (a) J acobs, T. L. In The Chemistry of Allenes; Landor, S. R., Ed.;
Academic Press: London, 1982; Vol. 2, Chapter 4.3. (b) Wojcicki, A.
Adv. Organomet. Chem. 1974, 12, 31. (c) Veber, M.; Doung, K. N. V.;
Gaudemer, F.; Gaudemer, A. J . Organomet. Chem. 1979, 18, 688. (d)
Lewis, L. N.; Huffman, J . C.; Caulton, K. G. J . Am. Chem. Soc. 1980,
102, 403. (e) Elsevier, C. J .; Kleijn, H.; Ruitenberg, K.; Vermeer, P. J .
C. S. J . Chem. Soc., Chem. Commun. 1983, 1529. (f) Tsuji, J .;
Watanabe, H.; Minami, I.; Shimizu, I. J . Am. Chem. Soc. 1985, 107,
2196. (g) Wojcicki, A.; Shuchart, C. E. Coord. Chem. Rev. 1990, 105,
35. (h) Cazes, B. Pure Appl. Chem. 1990, 62, 1867. (i) Tseng, T.-W.;
Wu, I.-Y.; Lin, Y.-C.; Chen, C.-T.; Cheng, M.-C.; Tsai, Y.-J .; Wang, Y.
Organometallics 1991, 10, 43. (j) Su, C.-C.; Chen, J .-T.; Lee, G.-H.;
Wang, Y. J . Am. Chem. Soc. 1994, 116, 4999.
Resu lts a n d Discu ssion
(2) (a) Breckenridge, S. M.; Taylor, N. J .; Carty, A. J . Organome-
tallics 1991, 10, 837. (b) Chen, J .-T.; Huang, T.-M.; Cheng, M.-C.; Lin,
Y.-C.; Wang, Y. Organometallics 1992, 11, 1761. (c) Blosser, P. W.;
Schimpff, D. G.; Gallucci, J . C.; Wojcicki, A. Organometallics 1993,
12, 1993. (d) Wouters, J . M. A.; Vrieze, K.; Elsevier, C. J . Organome-
tallics 1994, 13, 1510.
(3) (a) Krivykh, V. V.; Taits, E. S.; Petrovskii, P. V.; Struchkov, Y.
T.; Yanovskii, A. I. Mendeleev Commun. 1991, 103. (b) Casey, C. P.;
Yi, C. S. J . Am. Chem. Soc. 1992, 114, 6597. (c) Huang, T.-M.; Chen,
J .-T.; Lee, G.-H.; Wang, Y. J . Am. Chem. Soc. 1993, 115, 1170. (d)
Baize, M. W.; Furilla, J . L.; Wojcicki, A. Inorg. Chim. Acta 1994, 233,
1. (e) Huang, T.-M.; Hsu, R.-H.; Yang, C.-S.; Chen, J .-T.; Lee, G.-H.;
Wang, Y. Organometallics 1994, 13, 3657. (f) Plantevin, V.; Blosser,
P. W.; Gallucci, J . C.; Wojcicki, A. Organometallics 1994, 13, 3651. (g)
Baize, M. W.; Blosser, P. W.; Plantevin, V.; Schimpff, D. G.; Gallucci,
J . C.; Wojcicki, A. Organometallics 1996, 15, 164. (h) Doherty, S.;
Elsegood, M. R. J .; Clegg, W.; Waugh, M. Organometallics 1996, 15,
2688.
Su bstitu tion of a La bile Octa h ed r a l (η1-Allen yl)-
ir id iu m Com p lex. Because the octahedral (η1-allenyl)-
haloiridium complexes (OC-6-43)-Ir(X)2(PPh3)2(CO)(η1-
CHCCH2) (X ) Cl (1a ), Br (1b)) and (OC-6-54)-
(5) The η3-azatrimethylenemethane species M[η3-CH2C(NR)CH2] (R
) hydrocarbyl) is abbreviated as η3-aza-TMM. Accordingly, the
nomenclature for M[η3-CH2C(NH2)CH2] is N-protonated η3-azatri-
methylenemethane and for M[η3-CH2C(NRR′)CH2] (R ) alkyl, aryl) is
N-alkylated (or N-arylated) η3-azatrimethylenemethane.
(6) Tsai, F.-Y.; Hsu, R.-H.; Huang, T.-M.; Chen, J .-T.; Lee, G.-H.;
Wang, Y. J . Organomet. Chem. 1996, 520, 85.
(7) The IUPAC system is from: Nomenclature of Inorganic Chem-
istry, Recommendations; Leigh, G. J ., Ed.; Blackwell: Oxford, U.K.,
1990; pp 159-173.
(8) Hsu, R.-H.; Chen, J .-T.; Lee, G.-H.; Wang, Y. Organometallics,
in press.
(4) Yamamoto, Y.; Al-Masum, M.; Asao, N. J . Am. Chem. Soc. 1994,
116, 6019. (b) Yamamoto, Y.; Al-Masum, M.; Fujiwara, N.; Asao, N.
Tetrahedron Lett. 1995, 36, 2811.
S0276-7333(96)00262-2 CCC: $14.00 © 1997 American Chemical Society

Coordination of Aniline to an Ir Complex
Organometallics, Vol. 16, No. 7, 1997 1477
Sch em e 1
Ir(Br)(Cl)(PPh3)2(CO)(η1-CHCCH2) (1c) are found to be
inert to ammonia and amine, we prepared the labile
allenyliridium complex (OC-6-42)-Ir(Cl)(PPh3)2(OTf)-
(CO)(η1-CHCCH2) (2). Complex 2 is air-sensitive and
is subject to thermal decomposition in the solution. In
the presence of coordinating compounds such as aceto-
nitrile, benzylnitrile, and pyridine, the transformation
of 2 into {(OC-6-52)-Ir(Cl)(PPh3)2(L)(CO)(η1-CHCCH2)}-
(OTf) (L ) MeCN (3a ), PhCH2CN (3b), C6H5N (3c),
respectively) readily takes place.
F igu r e 1. ORTEP drawing of (OC-6-42)Ir(Cl)(PPh3)2-
(NHSO2Ph)(CO)(η1-CHCCH2) (4). All hydrogen atoms are
omitted for clarity.
Similarly, complex 2 can react with equimolar amounts
of ammonia, hydrazine, and various amines at 0 °C to
form {(OC-6-52)-Ir(Cl)(PPh3)2(L)(CO)(η1-CHCCH2)}(OTf)
(L ) NH3 (3d ), NH2NH2 (3e), MeNH2 (3f), EtNH2 (3g),
iPrNH2 (3h ), PhCH2NH2 (3i)) (Scheme 1). The com-
plexes 2 and 3a -i decompose in solution at 25 °C,
presumably due to the high lability of the nitrogen-
donor ligands on iridium. Complexes 3d ,g,i were
isolated by crystallization below 0 °C. Others were
primarily characterized by NMR spectroscopy. In the
typical case of formation of 3i, the sole signal of a singlet
at δ -9.5 in the 31P NMR spectrum indicates that the
reaction is exclusive and the two phosphines are in trans
positions. In the 1H NMR spectrum of 3i, two resonance
signals in a 2:1 ratio due to the allenyl ligand were
observed at δ 5.93 and 3.50. We assign a broad
resonance at δ 3.60 to the amino hydrogen and a
multiplet at δ 3.18 to the benzyl methylene hydrogen.
The carbonyl ligand is evidenced by IR spectroscopy,
showing a stretching band at 2062 cm-1. In addition,
the weak stretching of the linear allenyl group is at 1925
cm-1 and the NH peak at 3500 cm-1. The 13C NMR
data further support the assigned structure.
Sch em e 2
This formation of 3j proves that the reaction of 2 with
NH2SO2Ph is kinetically difficult. Weaker acids such
as CH3CO2H and PhCO2H take a couple of days to
accomplish the protonation under the same conditions.
Such experiments also confirm the amido character of
4 (Scheme 2).
The reaction of 2 with diethylamine results in com-
plicated products. It is assumed that diethylamine
probably could displace other ligands besides the triflate
ion. tert-Butylamine and NH2SO2Ph do not react with
2 under similar conditions. The former is considered
to be too bulky and the latter fails due to its weak
electron-donating ability; therefore, neither undergoes
substitution. Benzenesulfonamide is a strong nucleo-
phile and is able to replace the triflate ion of 2 to yield
(OC-6-42)-Ir(Cl)(PPh3)2(NHSO2Ph)(CO)(η1-CHCCH2) (4).
Complex 4 is stable in solution, and single crystals can
be grown from CHCl3/Et2O cosolvent. X-ray crystal-
lography affords the ORTEP drawing of 4 (Figure 1). It
displays an octahedral configuration in which the amido
ligand is trans to the η1-allenyl group. The allenyl
Rea ction of Com p lex 2 w ith An ilin e. Unlike the
aforementioned reactions of 2 with ammonia or amine,
when 2 reacts with aniline at 0 °C for 1 h, a light green
compound designated as 5d is produced in good yields.
The tetrafluoroborate salt of 5d can be obtained by first
reacting 1c and AgBF4 in situ, followed by adding
aniline. Complex 5d is stable in air and in solution.
Its 31P NMR spectrum shows two doublets at δ -11.2
and 10.1 with J P-P ) 3.1 Hz. In the 1H spectrum of
5d , the allenyl signals disappear. Instead, resonances
at δ 2.43 (Ha), 2.80 (Hb), 3.16 (Hc), 3.62 (Hd) and 10.14
(He) with one-hydrogen integration for each are de-
tected. The 2D H-H COSY spectrum exhibits Ha-Hd
and Hb-Hc couplings, and the 1D NOE shows that the
Hd signal gains 4.07% enhancement upon saturating He.
Accordingly, 5d is identified as the N-phenylated η3-
ligand is in a linear array with
C2-C3-C4 )
178(1)°, D(C2-C3) ) 1.27(1) Å, and D(C3-C4) )
1.32(1) Å.3e The single-bond distance of Ir-N and Ir-
N-S ) 120.0(3) confirm the amide feature.9 The NMR
studies show that protonation of 4 by HBF4 or CF3CO2H
instantaneously gives the amine derivative {(OC-6-42)-
Ir(Cl)(PPh3)2(NH2SO2Ph)(CO)(η1-CHCCH2)}(BF4) (3j).
(9) (a) Ru¨lke, R. E.; Kliphuis, D.; Elsevier, C. J .; Fraanje, J .; van
Leeuwen, P. W. N. M.; Vrieze, K. J . Chem. Soc., Chem. Commun. 1994,
1817. (b) Allen, S. R.; Beevor, R. G.; Green, M.; Norman, N. C.; Orpen,
A. G.; Williams, I. D. J . Chem. Soc., Dalton Trans. 1981, 2339. (c)
Merola, J . S. Organometallics 1989, 8, 2975. (d) Wolf, J .; Werner, H.
Organometallics 1987, 6, 1164.

1478 Organometallics, Vol. 16, No. 7, 1997
Chen et al.
Sch em e 3
azatrimethylenemethane complex {Ir(Cl)(PPh3)2(CO)-
[η3-CH2C(NHPh)CH2]}(OTf). The singlet at δ 10.14 is
assigned to the amino hydrogen He. The Hd and Hb
signals, which displays similar patterns, are ascribed
to the two syn hydrogen atoms and Ha and Hc to the
anti hydrogens.
The 13C NMR data at δ 169.6 and at δ 31.7, 39.5
correspond to the quaternary and secondary carbon
atoms. These data are consistent with those of the
known N-alkylated η3-aza-TMM iridium complexes.6
The C-H COSY spectrum indicates that the signal at
δ 31.7 correlates with Ha and Hd and that at δ 39.5
correlates with Hb and Hc. The diastereotopic data of
syn and anti hydrogens support the existence of the
CdN double bond. The exchange between syn and anti
hydrogens of 5d is not observed even at 60 °C. In
addition, the substituted aniline derivatives XC6H4NH2
(X ) F, NO2, OMe, Me) and other related compounds
such as Ph2NH and PhNH(Me) are also found to react
with 2 to yield the N-arylated η3-aza-TMM complexes
5a -c,e-g, respectively (Scheme 3). The reaction of 2
with diallylamine unexpectedly gives {Ir(Cl)(PPh3)2-
(CO)[η3-CH2C(N(C3H5)2)CH2]}(OTf) (5h ).
The molecular structures of 5f and 5g determined by
X-ray diffraction confirm our structural assignment for
5d . The ORTEP drawing of 5g is shown in Figure 2 as
an example. Complex 5g is in a distorted-trigonal-
bipyramidal geometry with the chloride and the carbo-
nyl at the axial sites, forming Cl-Ir-C1 ) 178.5(4)°.
The two phosphines on the equatorial plane have P1-
Ir-P2 ) 109.2(1)°. The organic ligand, which also sits
on the equatorial plane, is bonded to the metal center
in a η3 mode. The dihedral angle between the C2-C3-
C4 and C2-Ir-C4 planes is 47°. As a result, the central
carbon is more distant from the metal than the terminal
carbons with D(Ir-C2) ) 2.19(1) Å, D(Ir-C3) ) 2.50(1)
Å, and D(Ir-C4) ) 2.21(1) Å. The amino group is
attached to the central carbon C3 and approaches to the
chloride end. This finding is in contrast to the struc-
tures of the N-protonated η3-aza-TMM iridium com-
plexes, in which the amino substituent approaches the
carbonyl end. The N-C3 bond is substantially a double
bond. Besides, the rather planar relationship among
the six atoms of C2-6 and N, as well as the small
distortion angles of C5-N-C3-C4 (4.6(9)°) and C5-
N-C3-C2 (-4.2(8)°) reveal the good pπ-pπ interaction
in the NdC3 bond. The C3-C4 and C3-C2 bonds are
1.40(2) and 1.45(2) Å, respectively. Other data are
F igu r e 2. ORTEP drawing of {Ir(Cl)(PPh3)2(CO)[η3-CH2C-
(NMePh)CH2]}(OTf) (5g): (A) top view (all hydrogen atoms
are omitted for clarity); (B) side view (all hydrogen atoms
and the phosphino phenyls are omitted for clarity).
comparable with the structurally characterized N-
protonated or N-alkylated η3-aza-TMM iridium com-
plexes.
Mech an istic Stu dies of Hydr oan ilin ation of Com -
p lex 2. The difference in the reactivity toward nucleo-
philic addition between 2 and 1a -c is attributed to the
replacement of a labile triflate ligand for the inert
halide. The linear η1-allenyl ligand appears to be stable
to external nucleophilic attack. A general mechanism
for the nucleophilic addition of (η1-allenyl)iridium is
proposed in Scheme 4. In the first pathway, the
dissociation of the triflate anion from 2 leads to the
cationic η3-propargyl/allenyl species I, which is known
to be subject to nucleophilic addition at the central
carbon.4 In another pathway, the labile triflate ligand
in 2 may be first replaced by aniline to form the
nucleophile-ligated II. Complex II may form a product
of addition either via an intramolecular process or
through I.

Coordination of Aniline to an Ir Complex
Organometallics, Vol. 16, No. 7, 1997 1479
Sch em e 4
Sch em e 5
The NMR measurements with temperature variation
have supplied solid evidence for the occurrence of
substitution. At 220 K, 35 mg of 2 and equimolar
aniline was allowed to react in predried CDCl3.
A
metastable species designated as 3k which showed a
31P NMR peak at δ -15.7 was first formed. The
transformation was complete at 243 K. In comparison
with the data for 2 and 3, an η1-allenyl group and a
1
carbonyl group in 3k are evidenced by the H and 13C
NMR spectra. A relatively broad signal at δ 5.3 with
two-hydrogen integration is ascribed to the amino
hydrogens. The labeling experiments also shed light on
the structural assignment for 3k . The reaction of 2 and
equimolar 13C6H5NH2 gave the intermediate 13C6-3k .
The 13C signals of 13C6-3k were at δ 141.3 for the ipso,
δ 120.2 for the ortho, δ 126.5 for the para, and δ 129.5
for the meta carbons. Accordingly, 3k is identified as
the aniline-ligated η1-allenyl complex {(OC-6-42)-Ir(Cl)-
(PPh3)2(NH2Ph)(CO)(η1-CHCCH2)}(OTf).
Coordinating the nucleophile to a metal allows us to
facilitate addition to the allenyl ligand. Furthermore,
the metal mediator in such a nucleophile addition of the
coordinated allenyl group provides the implementation
of selectivity into the chemical transformation. Adding
1 equiv of benzylamine to 3k at 243 K followed by
raising the reaction temperature to 273 K resulted in a
mixture of the benzylamine-coordinated product 3i and
the N-phenylated η3-aza-TMM complex 5d in 1:1.3
relative yields. Complex 3i did not transform into the
N-alkylated η3-aza-TMM complex but slowly decom-
posed in the reaction solution. We also allowed equi-
molar amounts of aniline and 3i to mix at 25 °C. The
reaction was monitored by 1H NMR spectroscopy. After
3.5 h, 5d appeared at the expense of 3i, and the
conversion was 46%. After 7h, 5d accounted for 96%
stoichiometric molarity of iridium. We conclude that
there is reversible ligand exchange between complexes
3i and 3k . The equilibrium favors the former species
(Scheme 5). This is ascribed to the fact that the more
electron-donating benzylamine is a stronger ligand than
aniline.
direct external nucleophilic attack, 3k likely transforms
into 5d via an intramolecular process. Scheme 6 depicts
two possible mechanisms. The nucleophile-ligated
allenyliridium complex II may proceed either via the
metallacyclobutene III or via the π-allene complex IV
to accomplish the hydroanilination. In a general sense,
a step of hydrogen transfer and a step of nucleophilic
addition are involved in both paths, but with opposite
orders. Such a mechanism is attractive for the following
reasons. First, the formation of metallacyclobutene by
nucleophilic addition,4 insertion into the coordinated
allene,9 and the addition of anilide ligand to olefin are
all documented.10-12 Second, the relatively low basicity
of water, alcohol, or aniline may facilitate the hydrogen
transfer. With regard to ammonia, amide, and amine,
their higher basicity perhaps hinders the N-H activa-
tion and thus retards the addition. We find that adding
HBF4 to the reaction solution does not cause any
noticeable change of reactivity in such reactions, in
accord with the intramolecular hydrogen transfer. It
is difficult for us to explain why the reactions of 2 with
methylphenylamine or diallylamine of high basicity still
result in hydroamination.
Con clu d in g Rem a r k s
Adding aniline or its relatives to a labile octahedral
(η1-allenyl)iridium complex, (OC-6-42)-Ir(Cl)(PPh3)2-
(OTf)(CO)(η1-CHCCH2), at its central allenyl carbon
The reaction course from 3k to 5d is not so explicit.
Since 3i and 3k show distinct reactivities toward
addition, one would suspect the presence of a η3-
propargyl/allenyl intermediate which ought to be too
reactive to discern the addition of aniline from benzyl-
amine. Since the η1-allenyl ligand does not appeal to
(10) Casalnuovo, A. L.; Calabrese, J . C.; Milstein, D. J . Am. Chem.
Soc. 1988, 110, 6738.
(11) Villanueva, L. A.; Abboud, K. A.; Boncella, J . M. Organome-
tallics 1992, 11, 2963.
(12) Cowan, R. L.; Trogler, W. C. Organometallics 1987, 6, 2451.

1480 Organometallics, Vol. 16, No. 7, 1997
Chen et al.
Sch em e 6
(OC-6-42)-[Ir (Cl)(P P h 3)2(NC6H 5)(CO)(η1-CH CCH 2)]-
(OTf) (3c). Refer to the procedure for 3b. The isolated yield
of light green 3c was 61% (210 mg) after recrystallization. IR
leads to the formation of N-arylated iridium η3-azatri-
methylenemethane species. In contrast, this (η1-allen-
yl)iridium complex does not undergo addition with a
stronger nucleophile such as ammonia or amine but
suffers ligand substitution. A mechanistic study indi-
cates that precoordination of the added nucleophile
takes place first in these reactions. The coordinating
nucleophile thereby allows the metal to play a promi-
nent role in facilitating the addition process that
comprises the activation of the N-H bond and the
formation of the CdN bond, as well as to provide the
implementation of selectivity into the chemical trans-
formation.
(KBr pellet): νCdCdC 1923 cm-1, νCO 2055 cm-1
.
31P NMR
(CDCl3): δ -11.4. 1H NMR (CDCl3): δ 3.77 (2H, dt, J H-H
)
6.3 Hz, J P-H ) 3.6 Hz, CH2), 6.1 (1H, tt, J H-H ) 6.3 Hz, J P-H
) 3.2 Hz, CH), 6.7-8.5 (35H, m, phenyl H). 13C NMR
(CDCl3): δ 55.7 (s, CH), 69.8 (s, CH2), 118-155 (phenyl C),
159.7 (s, CO), 208.3 (t, J P-C ) 3.5 Hz, Câ). FAB MS (m/z):
898.5 (M+).
(OC-6-42)-[Ir (Cl)(P P h 3)2(NH 2NH 2)(CO)(η1-CH CCH 2)]-
(OTf) (3e). Refer to the procedure for 3b. The isolated yield
of 3e was 69% (138 mg) after recrystallization. IR (KBr
pellet): νCdCdC 1925 cm-1, νCO 2067 cm-1 31P NMR (CDCl3):
.
δ -11.2. 1H NMR (CDCl3): δ 3.44 (2H, br, NH), 3.60 (2H, dt,
J H-H ) 6.4 Hz, J P-H ) 3.7 Hz, CH2), 4.95 (2H, br, NH), 5.89
(1H, tt, J H-H ) 6.4 Hz, J P-H ) 3.0 Hz, CH), 7.2-7.9 (30H, m,
phenyl H). 13C NMR (CDCl3): δ 56.7 (t, J P-C ) 8 CH), 69.2
(s, CH2), 122-135 (phenyl C), 158.4 (t, J P-C ) 7.8 Hz, CO),
208.0 (s, Câ).
Exp er im en ta l Section
Gen er a l Con sid er a tion s. Commercially available re-
agents were purchased and used without purification. Sol-
vents were dried by means of standard procedures. The IR
spectra were recorded on a Bio-Rad FTS-40 spectrophotometer.
The NMR spectra were routinely measured on Bruker ACE-
200 and ACE-300 spectrometers. For the 31P NMR spectra,
the spectrometer frequency 81.015 or 121.49 MHz was em-
ployed, respectively, and the chemical shifts are given in ppm
(δ) relative to 85% H3PO4 in CDCl3. The corresponding
frequencies for 13C NMR spectra were at 50.32, 75.47, or 125.76
MHz for the various spectrometers.
(OC-6-42)-[Ir (Cl)(P P h 3)2(NH 2Me )(CO)(η1-CH CCH 2)]-
(OTf) (3f). The reaction of 2 (30 mg) and MeNH2 (1 equiv of
aqueous solution) was carried out in CDCl3 (0.5 mL) in an
NMR tube, and the complex 3f was characterized only by NMR
techniques. 31P NMR (CDCl3): δ -12.9. 1H NMR (CDCl3): δ
3.16 (2H, br, NH), 3.18 (3H, t, J H-H ) 6.2 Hz, CH3), 3.61 (2H,
dt, J H-H ) 6.2 Hz, J P-H ) 3.6 Hz, CH2), 5.97 (1H, tt, J H-H
)
6.2 Hz, J P-H ) 3.2 Hz, CH), 7.2-7.9 (30H, m, phenyl H). 13C
NMR (CDCl3): δ 32.2 (s, CH3), 55.1 (t, J P-C ) 7.5, CH), 69.2
(s, CH2), 118-135 (phenyl C), 158.4 (t, J P-C ) 6.9 Hz, CO),
207.6 (s, Câ).
Syn th esis a n d Ch a r a cter iza tion . (OC-6-42)-[Ir (Cl)-
(P P h 3)2(NCMe)(CO)(η1-CHCCH2)](OTf) (3a ). To a CDCl3
solution containing 2 (30 mg) was added 1 equiv of acetonitrile,
and the product was monitored by NMR. 31P NMR (CDCl3):
δ -12.6. 1H NMR (CDCl3): δ 1.81 (3H, s, CH3), 3.68 (2H, dt,
J H-H ) 6 Hz, J P-H ) 2.9 Hz, CH2), 5.72 (1H, tt, J H-H ) 6 Hz,
J P-H ) 3.1 Hz, CH), 6.7-7.8 (30H, m, phenyl H). 13C NMR
(CDCl3): δ 2.96 (s, CH3), 57.7 (s, CH), 70.7 (s, CH2), 116.9 (s,
CN), 123-134 (phenyl C), 156.7 (s, CO), 207.1 (t, J P-C ) 2.8
Hz, Câ).
(OC-6-42)-[Ir (Cl)(P P h 3)2(NH 2E t )(CO)(η1-CH CCH 2)]-
(OTf) (3g). Refer to the procedure for 3b. The isolated yield
of 3g was 53% (182 mg) after recrystallization. IR (KBr
pellet): νCdCdC 1923 cm-1, νCO 2059 cm-1 31P NMR (CDCl3):
.
δ -12.1. 1H NMR (CDCl3): δ 0.30 (3H, t, J H-H ) 6.9 Hz, CH3),
2.03 (2H, q, J H-H ) 6.9 Hz, CH2), 2.87 (2H, br, NH), 3.59 (2H,
dt, J H-H ) 6.4 Hz, J P-H ) 3.6 Hz, CH2), 6.00 (1H, tt, J H-H
)
6.4 Hz, J P-H ) 3.2 Hz, CH), 6.7-8.0 (30H, m, phenyl H). 13C
NMR (CDCl3): δ 17.4 (s, CH3), 42.0 (s, CH2), 55.1 (t, J P-C ) 8
Hz, CH), 69.4 (s, CH2), 117-135 (phenyl C), 158.6 (s, CO),
208.4 (t, J P-C ) 3.5 Hz, Câ). FAB MS (m/z): 864.4 (M+). Anal.
Calcd for IrC43H40O4ClNP2SF3: C, 50.93; H, 3.98; N, 1.38.
Found: C, 50.90; H, 3.98; N, 1.43.
(OC-6-42)-[Ir (Cl)(P P h 3)2(NCCH2P h )(CO)(η1-CHCCH2)]-
(OTf) (3b). To a mixture that contains 1c (250 mg, 0.28 mmol)
and AgOTf (1.1 equiv) was added 15 mL of N2-degassed dry
CH2Cl2 at -30 °C followed by benzylnitrile (32 µL, 1 equiv).
The reaction solution was stirred at 0 °C for 1 h. After removal
of AgBr, the reaction solution was concentrated. The addition
of dry Et2O to the solution resulted in a yellow solid product.
The isolated yield of 3b was 57% (173 mg) after recrystalli-
(OC-6-42)-[Ir (Cl)(P P h 3)2(NH 2iP r )(CO)(η1-CH CCH 2)]-
(OTf) (3h ). Refer to the procedure for 3f. 31P NMR (CDCl3):
δ -14.8. 1H NMR (CDCl3): δ 0.43 (6H, d, J H-H ) 6.1 Hz, CH3),
2.54 (1H, m, J H-H ) 6.1 Hz, CHMe2), 3.00 (2H, br, NH2), 3.44
(2H, m, CH2), 6.11 (1H, tt, J H-H ) 6.1 Hz, J P-H ) 3.2 Hz, CH),
7.2-7.9 (30H, m, phenyl H). 13C NMR (CDCl3): δ 23.4 (s,
CH3), 51.4 (s, CHMe2), 53.7 (t, J P-C ) 8.6 Hz, CH), 69.5 (s,
CH2), 125-135 (phenyl C), 159.6 (t, J P-C ) 7.1 Hz, CO), 207.3
(t, J P-C ) 2.6 Hz, Câ).
zation. IR (KBr pellet): νCdCdC 1926 cm-1, νCO 2073 cm-1 31P
.
NMR (CDCl3): δ -11.4. 1H NMR (CDCl3): δ 3.67 (2H, m,
CCH2), 3.68 (2H, s, PhCH2), 5.70 (1H, tt, J H-H ) 6.2 Hz, J P-H
) 2.7 Hz, CHC), 6.82-7.71 (35H, m, phenyl H). 13C NMR
(CDCl3): δ 58.4 (s, CH), 65.9 (s, CH2), 123-134 (phenyl C),
156.6 (t, J P-C ) 5.5 Hz, CO), 206.9 (s, Câ). FAB MS (m/ z):
819.4 (M+ - 117). Anal. Calcd for IrC49H40O4ClNP2SF3: C,
54.19; H, 3.71; N, 1.29. Found: C, 54.38; H, 3.86; N, 1.14.
(OC-6-42)-[Ir (Cl)(P P h 3)2(NH2CH2P h )(CO)(η1-CHCCH2)]-
(OTf) (3i). Refer to the procedure for 3b. The isolated yield

Coordination of Aniline to an Ir Complex
Organometallics, Vol. 16, No. 7, 1997 1481
of 3i was 63% (149 mg) after recrystallization. IR (KBr
was 52% (162 mg) after recrystallization. IR (KBr pellet): νCO
pellet): νCdCdC 1925 cm-1, νCO 2061 cm-1
.
31P NMR (CDCl3):
2036 cm-1 31P NMR (CDCl3): δ -11.5, -13.3 (J P-P ) 3.9 Hz).
.
δ -9.5. 1H NMR (CDCl3): δ 3.18 (2H, m, J H-H ) 7.2 Hz, J H-P
unresolved, PhCH2), 3.50 (2H, dt, J H-H ) 6.3 Hz, J P-H ) 3.6
Hz, CH2), 3.60 (2H, br, NH), 5.93 (1H, tt, J H-H ) 6.3 Hz, J P-H
) 3.1 Hz, CH), 6.9-7.86 (35H, m, phenyl H). 13C NMR
(CDCl3): δ 50.2 (s, PhCH2), 56.1 (t, J P-C ) 12 Hz, CH), 69.8
(s, CH2), 126-138 (phenyl C), 158.8 (s, CO), 208.1 (s, Câ). FAB
MS (m/z): 926.4 (M+). Anal. Calcd for IrC48H42O4ClNP2SF3:
C, 53.60; H, 3.94; N, 1.30. Found: C, 53.99; H, 3.76; N, 1.31.
(OC-6-42)-[Ir (Cl)(P P h 3)2(NH2SO2P h )(CO)(η1-CHCCH2)]-
(OTf) (3j). Into a CDCl3 solution containing 4 (30 mg) was
injected equimolar HBF4‚OEt2, and the NMR spectra were
measured. 31P NMR (CDCl3): δ -8.5. 1H NMR (CDCl3): δ
3.62 (2 H, dt, J H-H ) 6.2 Hz, J P-H ) 3.3 Hz, CH2), 4.99 (2H,
br, NH), 5.72 (1 H, tt, J H-H ) 6.2 Hz, J P-H ) 3.7 Hz, CH),
7.1-7.9 (35 H, m, phenyl H). 13C NMR (CDCl3): δ 58.3 (t,
J P-C ) 8.4, CH), 69.1 (s, CH2), 126-135 (phenyl C), 159.9 (s,
CO), 206.6 (s, Câ).
1H NMR (CDCl3): δ 2.40 (1H, m, Hanti), 2.67 (1H, m, Hsyn),
3.08 (1H, m, Hanti), 3.56 (1H, m, Hsyn), 3.80 (3H, s, OCH3), 6.7-
7.9 (34H, m, phenyl H), 10.01 (1H, s, NH). 13C NMR (CDCl3):
δ 31.0 (d, J P-C ) 50.6 Hz, CH2), 38.2 (d, J P-C ) 51.7 Hz, CH2),
55.6 (s, OCH3), 114-134 (phenyl C), 158.3 (s, ipso-MeOC6H4),
161.0 (dd, J P-C ) 7.1, 10.3 Hz, CO), 170.1 (s, Cc). FAB MS
(m/z): 942.4 (M+). Anal. Calcd for IrC48H42O5ClNP2SF3: C,
52.82; H, 3.88; N, 1.28. Found: C, 52.35; H, 3.86; N, 1.36.
{Ir (Cl)(P P h 3)2(CO)[η3-CH2C(NHP h )CH2]}(OTf) (5d ). To
a mixture containing 1c (250 mg, 0.28 mmol) and AgOTf (1.1
equiv) was added 15 mL of N2-degassed dry CH2Cl2 at -30 °C
followed by aniline (32 µL). The reaction solution was stirred
at 0 °C for 1 h. After AgOTf was removed by filtration, the
reaction solution was concentrated. The addition of degassed
dry Et2O to the solution resulted in light green solid product.
The yield was 71% (210 mg) after recrystallization. IR (KBr
pellet): νCO 2038 cm-1 31P NMR (CDCl3): δ -11.2, -13.3 (J P-P
.
) 3.1 Hz). 1H NMR (CDCl3): δ 2.43 (1H, m, Hanti), 2.80 (1H,
m, Hsyn), 3.16 (1H, m, Hanti), 3.62 (1H, m, Hsyn), 7.0-7.9 (35H,
m, phenyl H), 10.14 (1H, s, NH). 13C NMR (CDCl3): δ 31.7
(d, J P-C ) 53.8 Hz, CH2), 39.5 (d, J P-C ) 52.9 Hz, CH2), 128-
134 (phenyl C), 160.9 (dd, J P-C ) 7.1, 7.3 Hz, CO), 169.6 (s,
Cc). (13C6-5d : for d6-PhNH, δ 124.3 (t, J C-C ) 63.4 Hz, o-C),
126.7 (dt, J C-C ) 9, 54.3 Hz, p-C), 129.5 (t, J C-C ) 54.3 Hz,
m-C), 135.9 (dt, J C-C ) 9.1, 63.4 Hz, ipso-C)). FAB MS (m/z):
912.4 (M+).
(OC-6-42)-[Ir (Cl)(P P h 3)2(NH 2P h )(CO)(η1-CH CCH 2)]-
(OTf) (3k ). Into a CDCl3 solution containing 2 (35 mg) was
injected equimolar aniline at 223 K. The NMR spectra were
taken at 243 K. 31P NMR (CDCl3): δ -15.7. 1H NMR
(CDCl3): δ 3.44 (2H, br, NH), 3.53 (2H, dt, J H-H ) 6.4 Hz,
J P-H ) 3.7 Hz, CH2), 5.30 (2H, br, NH), 5.98 (1H, tt, J H-H
)
6.4 Hz, J P-H ) 3.0 Hz, CH), 6.69-7.95 (30H, m, phenyl H).
13C NMR (CDCl3): δ 53.6 (t, J P-C ) 8, CH), 66.0 (s, CH2), 122-
135 (phenyl C), 158.2 (t, J P-C ) 7.8 Hz, CO), 206.3 (s, Câ).
(OC-6-42)-[Ir (Cl)(P P h 3)2(NH213C6-P h )(CO)(η1-CHCCH2)]-
(OTf) (13C6-3k ). Refer to the procedure for 3k , except with
13C-labeled aniline. 13C NMR (CDCl3): δ 53.6 (t, J P-C ) 8,
CH), 66.0 (s, CH2), 120.2 (o-C of aniline), 126.5 (p-C of aniline),
129.5 (m-C of aniline), 122-135 (phenyl C of PPh3), 141.3
(ipso-C of aniline), 158.2 (t, J P-C ) 7.8 Hz, CO), 206.3 (s, Câ).
(OC-6-42)-Ir (Cl)(P P h 3)2(NHSO2P h )(CO)(η1-CHCCH2) (4).
To a mixture containing 1c (355 mg, 0.37 mmol) and NaNHSO2-
Ph (80 mg, 1.2 equiv) was added 18 mL of N2-degassed dry
CHCl3 by the vacuum-transfer technique. The reaction solu-
tion was sonicated at 0 °C for 40 min. After NaOTf was
removed by filtration, the reaction solution was concentrated.
The addition of degassed dry Et2O to the solution resulted in
a whitish yellow product. The isolated yield of 4 was 91% (325
{Ir (CI)(P P h 3)2(CO)[η3-CH2C(NHC6H4Me)CH2]}(OTf) (5e).
Refer to the procedure for 5d . The isolated yield of 5e was
61% (215 mg) after recrystallization. IR (KBr pellet): νCO 2035
cm-1 31P NMR (CDCl3): δ -11.5, -12.8 (J P-P ) 3.3 Hz). 1H
.
NMR (CDCl3): δ 2.08 (3H, s, CH3), 2.28 (1H, m, Hsyn), 2.39
(1H, m, Hanti), 3.10 (1H, m, Hanti), 3.65 (1H, m, Hsyn), 7.1-7.9
(34H, m, phenyl H), 10.09 (1H, s, NH). 13C NMR (CDCl3): δ
29.9 (d, J P-C ) 49.7 Hz, CH2), 37.7 (d, J P-C ) 51.3 Hz, CH2),
117-135 (phenyl C), 161.4 (dd, J P-C ) 6.9, 9.9 Hz, CO), 172.3
(s, Cc). FAB MS (m/z): 926.4 (M+). Anal. Calcd for
IrC48H42O4ClNP2SF3: C, 53.60; H, 3.94; N, 1.30. Found: C,
53.42; H, 3.93; N, 1.00.
{Ir (Cl)(P P h 3)2(CO)[η3-CH2C(NP h 2)CH2]}(OTf) (5f). Re-
fer to the procedure for 5d . The isolated yield of 5f was 76%
(191 mg) after recrystallization. IR (KBr pellet): νCO 2044
mg) after recrystallization. IR (KBr pellet): νCdCdC 1920 cm-1
νCO 2064 cm-1 31P NMR (CDCl3): δ -16.3. 1H NMR
,
.
cm-1 31P NMR (CDCl3): δ -13.1. 1H NMR (CDCl3): δ 2.47
.
(CDCl3): δ 2.4 (1H, s, NH), 3.56 (2H, dt, J H-H ) 6.4 Hz, J P-H
) 3.6 Hz, CH2), 6.05 (1H, tt, J H-H ) 6.4 Hz, J P-H ) 3.2 Hz,
CH), 7.0-7.9 (35H, m, phenyl H). 13C NMR (CDCl3): δ 58.3
(t, J P-C ) 8, CH), 67.1 (s, CH2), 125-145 (phenyl C), 158.6 (s,
CO), 206.3 (s, Câ). FAB MS (m/z): 819.4 (M+ - PhSO2NH).
{Ir (Cl)(P P h 3)2(CO)[η3-CH2C(NHC6H4F )CH2]}(OTf) (5a ).
Refer to the procedure for 5d . IR (KBr pellet): νCO 2039 cm-1
.
31P NMR (CDCl3): δ -11.5, -13.2 (J P-P ) 3.4 Hz). 1H NMR
(CDCl3): δ 2.44 (1H, m, Hanti), 2.65 (1H, m, Hsyn), 3.15 (1H, m,
H
anti), 3.57 (1H, m, Hsyn), 6.9-7.9 (34H, m, phenyl H), 10.08
(1H, s, NH). 13C NMR (CDCl3): δ 32.3 (d, J P-C ) 51.0 Hz,
CH2), 39.6 (d, J P-C ) 48.6 Hz, CH2), 117-135 (phenyl C), 159.1
(ipso-FC6H4), 161.1 (m, CO), 172.3 (s, Cc). FAB MS (m/z):
930.5 (M+). Anal. Calcd for IrC47H39O4ClNP2SF4: C, 52.26;
H, 3.64; N, 1.30. Found: C, 52.29; H, 3.90; N, 1.20.
{Ir (Cl)(P P h 3)2(CO)[η3-CH 2C(NH C6H 4NO2)CH 2]}(OTf)
(5b). Refer to the procedure for 5d . The yield of 5b was 77%
(187 mg) after recrystallization. IR (KBr pellet): νCO 2041
cm-1
.
31P NMR (CDCl3): δ -11.6, -13.3 (J P-P unresolved).
1H NMR (CDCl3): δ 2.55 (1H, m, Hanti), 2.85 (1H, m, Hsyn),
3.39 (1H, m, Hanti), 3.72 (1H, m, Hsyn), 7.1-8.1 (34H, m, phenyl
H), 10.41 (1H, s, NH). 13C NMR (CDCl3): δ 34.7, 43.8 (br,
CH2), 114-134 (phenyl C), 145.4 (ipso-NO2C6H4), 160.8 (m,
CO), 166.8 (s, Cc). FAB MS (m/z): 957.4 (M+). Anal. Calcd
for IrC47H39O6ClN2P2SF3: C, 51.02; H, 3.55; N, 2.53. Found:
C, 50.43; H, 3.57; N, 2.33.
{Ir (Cl)(P P h 3)2(CO)[η3-CH 2C(NH C6H 4OMe)CH 2]}(OTf)
(5c). Refer to the procedure for 5d . The isolated yield of 5c

1482 Organometallics, Vol. 16, No. 7, 1997
Ta ble 1. X-r a y Cr ysta l P a r a m eter s a n d Da ta Collection
Chen et al.
4
5f
5g
formula
fw
cryst dimens, mm
space group
a, Å
IrClSP2O3NC46H39‚2CH2Cl2
IrClSP2F3O4NC53H44
IrClSP2F3O4NC48H41‚0.5CH2Cl2
1145.36
0.04 × 0.40 × 0.45
P21/n
1137.60
0.04 × 0.08 × 0.15
P21/c
12.216(1)
35.803(6)
11.287(2)
90
98.07(1)
90
4888(1)
4
1116.99
0.20 × 0.30 × 0.50
Pbcn
10.210(2)
20.265(3)
23.677(6)
90
101.02(2)
90
4809(2)
4
1.582
37.838(9)
10.728(3)
23.661(6)
90
90
90
9605(4)
8
1.545
b, Å
c, Å
R, deg
â, deg
γ, deg
V, Å3
Z
F(calcd), Mg m-3
F(000)
1.546
2268
2278
4441
radiation; λ, Å
Mo KR; 0.7107
Mo KR; 0.7107
Mo KR; 0.7107
T, K
298
298
298
µ, mm-1
transmission
max 2θ, deg
hkl
no. of rflns measd
no. of rflns obsd
no. of variables
R(F)
2.96
0.58-1.0
50
(12,24,28
8440
5091 (>2.0σ)
551
2.94
0.92-1.0
45
(13,38,12
6358
2950 (>2.0σ)
595
2.99
0.86-1.0
45
40,11,25
6253
3594 (>2.0σ)
550
0.037
0.073
0.052
Rw(F)
0.037
0.074
0.051
S
1.30
2.25
1.93
(∆/σ)max
0.0137
0.1350
0.0308
Ta ble 2. Selected Bon d Dista n ces (Å) a n d An gles (d eg)
(OC-6-42)-Ir(Cl)(PPh3)2(NHSO2Ph)(CO)(η1-CHCCH2) (4)
Ir-Cl(1)
Ir-P1
Pt-P2
Ir-N
2.407(2)
2.402(2)
2.410(2)
2.158(6)
Ir-C1
Ir-C2
C1-O1
C2-C3
1.829(8)
2.079(7)
1.145(9)
1.27(1)
C3-C4
S-N
S-C5
1.32(1)
S-O2
S-O3
1.435(6)
1.453(6)
1.580(6)
1.772(8)
Cl1-Ir-P1
Cl1-Ir-P2
Cl1-Ir-C2
Cl1-Ir-C2
Cl1-Ir-N
P1-Ir-P2
P1-Ir-C1
90.62(7)
85.75(7)
178.9(2)
91.9(2)
85.0(2)
174.58(7)
90.3(2)
P1-Ir-C2
P1-Ir-N
P2-Ir-C1
P2-Ir-C2
P2-Ir-N
C1-Ir-N
C2-Ir-N
87.9(2)
90.8(2)
93.3(2)
88.2(2)
92.8(2)
95.6(3)
176.7(3)
Cl-Ir-C2
N-S-C5
N-S-O2
N-S-O3
C5-S-O2
C5-S-O3
O3-S-O2
87.5(3)
104.3(3)
110.4(4)
112.2(3)
108.2(4)
106.6(4)
114.5(4)
Ir-N-S
120.0(3)
177.5(6)
128.4(6)
178(1)
120.4(7)
119.1(7)
Ir-C1-O1
Ir-C2-C3
C2-C3-C4
S-C5-C6
S-C5-C10
{Ir(Cl)(PPh3)2(CO)[η3-CH2C(NPh2)CH2]}(OTf) (5f)
Ir-Cl
Ir-P1
Ir-P2
Ir-C1
2.376(9)
2.422(8)
2.403(8)
1.86(3)
Ir-C2
Ir-C3
Ir-C4
C3-N
2.18(3)
2.54(3)
2.15(3)
1.31(3)
C5-N
1.46(3)
1.44(4)
1.05(4)
C2-C3
C3-C4
1.41(4)
1.54(4)
C11-N
C1-O1
Cl-Ir-P1
Cl-Ir-P2
Cl-Ir-Cl
Cl-Ir-C2
Cl-Ir-C3
Cl-Ir-C4
P1-Ir-P2
P1-Ir-C1
P1-Ir-C2
P1-Ir-C3
89.4(3)
91.8(3)
174(1)
88.5(8)
76.7(7)
93.9(8)
109.2(3)
92.7(9)
156.8(7)
123.5(6)
P1-Ir-C4
P2-Ir-Cl
P2-Ir-C2
P2-Ir-C3
P2-Ir-C4
C1-Ir-C2
C1-Ir-C3
C1-Ir-C4
C2-Ir-C3
91.5(7)
93(1)
94.0(7)
125.4(6)
158.6(7)
87(1)
97(1)
80(1)
33.9(9)
C2-Ir-C4
C3-Ir-C4
C3-N-C5
C3-N-C11
C5-N-C11
Ir-C1-O1
Ir-C2-C3
Ir-C3-C4
Ir-C3-C2
66(1)
37.3(9)
118(2)
118(2)
124(2)
158(3)
87(2)
Ir-C4-C3
Ir-C3-N
85(2)
136(2)
105(2)
125(3)
128(2)
120(3)
123(3)
114(2)
117(3)
C2-C3-C4
C2-C3-N
C4-C3-N
N-C5-C6
N-C5-C10
N-C11-C12
N-C11-C16
61.4(1)
59(2)
{Ir(Cl)(PPh3)2(CO)[η3-CH2C(NMePh)CH2]}(OTf) (5g)
Ir-Cl
Ir-P1
Ir-P2
Ir-C1
2.390(4)
2.429(4)
2.416(3)
1.86(1)
Ir-C2
Ir-C3
Ir-C4
C3-N
2.19(1)
2.50(1)
2.21(1)
1.32(2)
C5-N
C6-N
C1-O1
1.46(2)
1.47(2)
1.05(2)
C2-C3
C3-C4
1.40(2)
1.45(2)
Cl-Ir-P1
Cl-Ir-P2
Cl-Ir-C1
Cl-Ir-C2
Cl-Ir-C3
Cl-Ir-C4
P1-Ir-P2
P1-Ir-C1
P1-Ir-C2
92.9(1)
86.3(1)
178.5(4)
88.7(3)
74.6(3)
88.8(4)
109.2(1)
88.2(4)
156.7(4)
P1-Ir-C3
P1-Ir-C4
P2-Ir-Cl
P2-Ir-C2
P2-Ir-C3
P2-Ir-C4
C1-Ir-C2
C1-Ir-C3
C1-Ir-C4
124.9(3)
92.9(3)
94.4(4)
94.1(3)
122.7(3)
157.5(3)
89.9(5)
103.9(5)
90.1(5)
C2-Ir-C3
C2-Ir-C4
C3-Ir-C4
C3-N-C5
C3-N-C6
C5-N-C6
Ir-C1-O1
Ir-C2-C3
Ir-C3-C4
33.8(4)
63.8(5)
35.2(4)
123(1)
120(1)
116(1)
173(1)
85.1(8)
61.4(6)
Ir-C3-C2
Ir-C4-C3
Ir-C3-N
C2-C3-C4
C2-C3-N
C4-C3-N
N-C6-C7
N-C6-C11
61.0(7)
83.4(7)
137(1)
110(1)
126(1)
123(1)
118(1)
121(1)
X-r a y Cr ysta llogr a p h ic An a lysis. Diffraction data were
measured at 298 K on a Nonius CAD-4 diffractometer with
graphite-monochromated Mo KR radiation. Cell parameters
were determined by a least-squares fit on 25 reflections.
Intensity data were corrected for absorption on the basis of
an experimental ψ rotation curve. The refinement procedure

Coordination of Aniline to an Ir Complex
Organometallics, Vol. 16, No. 7, 1997 1483
was by a full-matrix least-squares method including all the
non-hydrogen atoms anisotropically. Hydrogen atoms were
fixed at the ideal geometry and the C-H distance of 1.0 Å;
their isotopic thermal parameters were fixed to the values of
the attached carbon atoms at the convergence of the isotropic
refinement. Atomic scattering factors were taken from ref 13.
Computing programs are from the NRCC SDP VAX package.14
Crystallographic data and selected bond parameters for 4, 5f,
and 5g are collected in Tables 1 and 2. Other detailed data
are supplied in the Supporting Information.
Ack n ow led gm en t. We thank the National Science
Council, Taiwan, ROC, for financial support.
Su p p or tin g In for m a tion Ava ila ble: Complete listings
of crystal data, bond lengths and angles, atomic coordinates,
and thermal parameters and figures giving fully labeled
ORTEP drawings for 4, 5f, and 5g (32 pages). Ordering
information is given on any current masthead page.
(13) International Tables for X-ray Crystallography; Kynoch Press:
Birmingham, U.K., 1974; Vol. IV.
(14) NRC VAX: Gabe, E. J .; LePage, Y.; Charland, J .-P.; Lee, F. L.;
White, P. S. J . Appl. Crystallogr. 1989, 22, 384.
OM9602623