Cationic indium alkyl complexes incorporating aminotroponiminate ligands

Article abstract of DOI:10.1021/om010578x

The synthesis and structures of indium complexes incorporating the bidentate monoanionic ligand N,N′-diisopropylaminotroponiminate (ⁱPr₂-ATI) are described. The reaction of InCl₃ with Li[ⁱPr₂-ATI] yields (ⁱPr₂-ATI)InCl₂ (3), which is converted to (ⁱPr₂-ATI)InMe₂ (4) by reaction with MeLi; 4 is also formed by the reaction of InMe₃ with (ⁱPr₂-ATI)H. The reaction of 4 with [Ph₃C] [B(C₆F₅)₄] at 23 °C yields the diimine complex [{1,2-(NⁱPr)₂-5-CPh₃-cyclohepta-3,6-diene}InMe ₂] [B(C₆F₅)₄] (5) via addition of Ph₃C^- to the C5 carbon of 4. Thermolysis of 5 (75 °C) yields [(ⁱPr₂-ATI)InMe] [B(C₆F₅)₄] (6) and Ph₃CMe. 6 was isolated as the chlorobenzene solvate 6·PhCl. An X-ray diffraction study shows that there are two independent cations in the asymmetric unit of 6·PhCl. One cation (In(1)) is ion-paired with two B(C₆F₅)₄^- anions, while the second cation is complexed with two PhCl molecules and is disordered between two equally occupied positions (In(2) and In(3)). Dative In-ClPh bonding and PhCl/ATI π-stacking interactions contribute to the PhCl coordination in 6·PhCl. The reaction of 4 with B(C₆F₅)₃ yields [(ⁱPr₂-ATI)InMe] [MeB(C₆F₅)₃] (7), which decomposes slowly at 23 °C by C₆F₅^- transfer reactions. The reaction of 4 with [HNMe₂Ph] [B(C₆F₅)₄] yields the labile amine adduct [(ⁱPr₂-ATI)In(Me)(NMe₂Ph)] [B(C₆F₅)₄] (10).

Full text of DOI:10.1021/om010578x

Organometallics 2002, 21, 1167-1176
1167
Ca tion ic In d iu m Alk yl Com p lexes In cor p or a tin g
Am in otr op on im in a te Liga n d s
Fabien Delpech,† Ilia A. Guzei,‡ and Richard F. J ordan*,†
Department of Chemistry, The University of Chicago, 5735 S. Ellis Avenue,
Chicago, Illinois 60637, and Department of Chemistry, Iowa State University,
Ames, Iowa 50011
Received J une 28, 2001
The synthesis and structures of indium complexes incorporating the bidentate monoanionic
ligand N,N′-diisopropylaminotroponiminate (iPr2-ATI) are described. The reaction of InCl3
with Li[iPr2-ATI] yields (iPr2-ATI)InCl2 (3), which is converted to (iPr2-ATI)InMe2 (4) by
reaction with MeLi; 4 is also formed by the reaction of InMe3 with (iPr2-ATI)H. The reaction
of 4 with [Ph3C][B(C6F5)4] at 23 °C yields the diimine complex [{1,2-(NiPr)2-5-CPh3-cyclohepta-
3,6-diene}InMe2][B(C6F5)4] (5) via addition of Ph3C+ to the C5 carbon of 4. Thermolysis of 5
(75 °C) yields [(iPr2-ATI)InMe][B(C6F5)4] (6) and Ph3CMe. 6 was isolated as the chlorobenzene
solvate 6‚PhCl. An X-ray diffraction study shows that there are two independent cations in
-
the asymmetric unit of 6‚PhCl. One cation (In(1)) is ion-paired with two B(C6F5)4 anions,
while the second cation is complexed with two PhCl molecules and is disordered between
two equally occupied positions (In(2) and In(3)). Dative In-ClPh bonding and PhCl/ATI
π-stacking interactions contribute to the PhCl coordination in 6‚PhCl. The reaction of 4 with
-
B(C6F5)3 yields [(iPr2-ATI)InMe][MeB(C6F5)3] (7), which decomposes slowly at 23 °C by C6F5
transfer reactions. The reaction of 4 with [HNMe2Ph][B(C6F5)4] yields the labile amine adduct
[(iPr2-ATI)In(Me)(NMe2Ph)][B(C6F5)4] (10).
In tr od u ction
which undergo associative ligand exchange. The (iPr2-
ATI)AlR+ cations catalyze the dimerization of terminal
alkynes by an insertion/σ-bond metathesis mechanism
and initiate the polymerization of isobutylene and
propylene oxide. The dinuclear hydride cation {(iPr2-
Neutral group 13 EX3 and ER3 complexes are widely
used as Lewis acids, alkylating agents and reducing
agents.1-3 Cationic group 13 complexes are of interest
for these and other applications because the charge may
enhance the Lewis acidity of the metal center and
influence the reactivity of the E-X or E-R groups.4-7
Low-coordinate cations are particularly attractive for
applications in catalysis.8,9 We have described the
chemistry of cationic aluminum complexes (iPr2-ATI)-
AlR+ which are stabilized by the N,N′-diisopropyl-
aminotroponiminate ligand (iPr2-ATI) and can be iso-
(6) (a) Cosle´dan, F.; Hitchcock, P. B.; Lappert, M. F. Chem. Commun.
1999, 705. (b) Atwood, D. A.; J egier, J . Inorg. Chem. 1996, 35, 4277.
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H.; Henderson, M. J .; Raston, C. L. J . Organomet. Chem. 1990, 384,
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E. J . J . Am. Chem. Soc. 1996, 118, 5502.
lated as the B(C6F5)4 salts.10 These formally three-
-
coordinate species are potent Lewis acids and form
complexes with amines, phosphines, acetone, CH3CN,
neutral Al alkyls (via Me bridging), and chlorobenzene,
† University of Chicago.
‡ Iowa State University.
(1) (a) Paquette, L. A. In Encyclopedia of Reagents for Organic
Synthesis; Wiley & Sons: New York, 1995; p 153 and p 645. (b) Eisch,
J . J . In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone,
F. G. A., Wilkinson, G., Eds.; Elsevier: Oxford, UK, 1995; Vol 11,
Chapter 6. (c) Kennedy, J . P.; Marechal, E. Carbocationic Polymeri-
zation; Wiley-Interscience: New York, 1982. (d) Olah, G. A. In Friedel-
Crafts Chemistry; Wiley & Sons: New York, 1972; p 215.
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M. P.; J ordan, R. F. J . Am. Chem. Soc. 2000, 122, 274. (e) J ordan, R.
F.; Aeilts, S. L.; Coles, M. P.; Dagorne, S. G.; Ihara, E. Polym. Mater.
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(b) Loh, T. P.; Pei, J .; Lin, M. Chem. Commun. 1996, 2315. (c) Chan,
T. H.; Yang, Y. J . Am. Chem. Soc. 1999, 121, 3228.
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1998, 927.
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5908. (b) Dohmeier, C.; Schno¨ckel, H.; Robl, C.; Schneider, U.; Ahlrichs,
R. Angew. Chem., Int. Ed. Engl. 1993, 32, 1655. (c) Bochmann, M.;
Dawson, D. M. Angew. Chem., Int. Ed. Engl. 1996, 35, 2226. (d) Burns,
C. T.; Stelck, D. S.; Shapiro, P. J .; Vij, A.; Kunz, K.; Kehr, G.; Concolino,
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(10) (a) Ihara, E.; Young, V. G.; J ordan, R. F. J . Am. Chem. Soc.
1998, 120, 8277. (b) Korolev, A. V.; Guzei, I. A.; J ordan, R. F. J . Am.
Chem. Soc. 1999, 121, 11605. (c) Korolev, A. V.; Delpech, F.; Dagorne,
S.; Guzei, I. A.; J ordan, R. F. Organometallics 2001, 20, 3367. (d)
Korolev, A. V.; Ihara, E.; Guzei, I. A.; Young, V. G.; J ordan, R. F. J .
Am. Chem. Soc. 2001, 123, 8291.
10.1021/om010578x CCC: $22.00 © 2002 American Chemical Society
Publication on Web 02/20/2002

1168 Organometallics, Vol. 21, No. 6, 2002
Delpech et al.
+
Sch em e 1
ATI)Al}2H3 polymerizes methyl methacrylate. The
most prominent reaction of (iPr2-ATI)AlCH2CH2R+ spe-
cies with unsaturated substrates is â-H transfer to the
coordinated substrate.
Here we describe initial studies of the analogous
cationic indium aminotroponiminate species (iPr2-
ATI)InMe+.10c Indium and Al differ in several key
respects: In is significantly larger than Al (covalent
radii 1.50 vs 1.25 Å), In-C bonds are significantly
weaker (38 vs 66 kcal/mol) and less polar than Al-C
bonds (Pauling ø values: In 1.78; Al 1.61), and In Lewis
acids are generally weaker than the corresponding Al
Lewis acids.11 Indium alkyls are generally less reactive
than Al alkyls but do undergo alkane elimination and
insertion reactions. For example, InR3 (R ) Me, Et)
complexes react with phenylacetylene to yield R2In(Ct
CPh) products, and In(CH2CH2CH2CH2CHdCH2)3 un-
dergoes slow cyclization to In(cyclopentylmethyl)3.12,13
The long-term objective of the present work is to probe
how these differences in elemental properties influence
the structures and reactivity of Al and In (iPr2-ATI)-
imine ((iPr2-ATI)H, 1) with BuLi (Et2O, -78 °C) yields
Li[iPr2-ATI] (2), which can be isolated in high yield as
an orange powder and is a convenient source of the iPr2-
ATI- ligand. The reaction of 2 with 1 equiv of InCl3
yields (iPr2-ATI)InCl2 (3) as a pale yellow solid in 64%
yield (Scheme 1). Alkylation of 3 with 2 equiv of MeLi
(Et2O, -78 °C) affords (iPr2-ATI)InMe2 (4). Compound
4 is also formed by the reaction of InMe3 with 1 equiv
of 1. Compound 4 is isolated as a yellow crystalline solid
by crystallization from cold pentane. Compounds 3 and
4 are stable in air and in wet NMR solvents for several
days. The 1H and 13C NMR spectra of 3 and 4 are
consistent with C2v-symmetric structures and sym-
metrical bidentate coordination of the aminotropon-
iminate ligand.
i
ER+ species. Dias has pioneered the use of the Pr2-ATI
ligand in main group chemistry and has prepared the
bis-aminotroponiminate complex (Me2-ATI)2InCl.14 The
tropolonate complex {C7H5O2}InMe2 has also been
prepared.15
Several classes of indium cations are known, includ-
ing In(H2O)6 and related aquo species,16 four-, five-,
3+
and six-coordinate InX2Ln+ complexes (X ) halide; n )
2-4; L ) O, N, or P donor),17 and higher coordinate
+
InX2Ln complexes incorporating crown ether or other
multidentate ligands.18 Additionally, and most relevant
to the present work, several “InR2+” species have been
+
characterized. The InMe2 cation is stable in aqueous
solution,19 and in the solid state InR2+ cations typically
exhibit tetragonal bipyramidal structures with a nearly
Molecu la r Str u ctu r es of 3 a n d 4. The molecular
structures of 3 and 4 were determined by X-ray crystal-
lography (Figures 1, 2 and Tables 1, 2). In both cases,
there are two independent molecules in the asymmetric
unit which have very similar structures; average metri-
cal parameters for the two molecules are referred to in
the following discussion. Both 3 and 4 adopt monomeric
structures with distorted tetrahedral geometry at In.
+
linear InR2 core and four weakly coordinated equato-
rial ligands.20,21
Resu lts a n d Discu ssion
Neu tr al In diu m Am in otr opon im in ate Com plexes.
The reaction of N-isopropyl-2-(isopropylamino)tropon-
i
The Pr2-ATI ligands in both species are coordinated in
a symmetrical fashion, and the ATI π-systems are
delocalized. The major structural difference between 3
and 4 is that the Me-In-Me angle in 4 (128.2° av) is
ca. 22° larger than the Cl-In-Cl angle in 3 (106.3° av).
This difference reflects the higher p character in the In
orbitals used in In-Cl bonding compared to In-Me
bonding due to the higher electronegativity of Cl com-
pared to Me (Bent’s rule).22,23 The N-In-N bite angle
(11) Downs, A. J . In Chemistry of Aluminium, Gallium, Indium and
Thallium; Downs, A. J ., Ed.; Chapman & Hall: London, UK, 1993; p
1.
(12) (a) Alcock, N. W.; Degnan, I. A.; Roe, S. M.; Wallbridge, M. G.
H. J . Organomet. Chem. 1991, 414, 285. (b) J effery, E. A.; Mole, T. J .
Organomet. Chem. 1968, 11, 393.
(13) Dolzine, T. W.; Oliver, J . P. J . Organomet. Chem. 1974, 78, 165.
(14) (a) Dias, H. V. R.; J in, W. Inorg. Chem. 1996, 35, 6546. (b) Dias,
H. V. R.; J in, W.; Ratcliff, R. E. Inorg. Chem. 1995, 34, 6100.
(15) Waller, I.; Halder, T.; Schwarz, W.; Weidlein, J . J . Organomet.
Chem. 1982, 232, 99.
(16) (a) Tuck, D. G. In Comprehensive Coordination Chemistry;
Gillard, R. D., McCleverty, J . A., Eds.; Pergamon: Oxford, UK, 1987;
Vol. 3, p 153. (b) Taylor, M. J .; Brothers, P. J . In Chemistry of
Aluminium, Gallium, Indium and Thallium; Downs, A. J ., Ed.;
Chapman & Hall: London, UK, 1993; p 142. (c) Brown, P. L.; Ellis, J .;
Sylva, R. N. J . Chem. Soc., Dalton Trans. 1982, 1911.
(17) (a) Sigl, M.; Schier, A.; Schmidbaur, H. Eur. J . Chem. 1998,
203. (b) Robinson, W. T.; Wilkins, C, J .; Zeying, Z. J . Chem. Soc., Dalton
Trans. 1990, 219. (c) Canty, A. J .; Titcombe, L. A.; Skelton, B. W.;
White, A. H. J . Chem. Soc., Dalton Trans. 1988, 35.
(20) (a) Me2InBr: Hausen, H. D.; Mertz, K.; Weidlein, J .; Schwarz,
W. J . Organomet. Chem. 1975, 93, 291. (b) [iPr2In(THF)2][BF4]:
Neumuller, B.; Gahlmann, Y. T. J . Organomet. Chem. 1991, 414, 271.
(c) [(mesityl)2In][BF4]: Gahlmann, Y. T.; Neumuller, B. Z. Anorg. Allg.
Chem. 1994, 620, 847. (d) Me2In(OAc): Einstein, F. W. B.; Gilbert, M.
M.; Tuck, D. G. J . Chem. Soc., Dalton Trans. 1973, 248.
(21) See also: (a) Greenwood, N. N.; Thomas, B. S.; Waite, D. W. J .
Chem. Soc., Dalton Trans. 1975, 299. (b) Poland, J . S.; Tuck, D. G. J .
Organomet. Chem. 1972, 42, 315. (c) Gynane, M. J . S.; Waterworth,
L. G.; Worrall, J . J . Organomet. Chem. 1972, 43, 257. (d) Brill, T. B.
Inorg. Chem. 1976, 15, 2558. (e) Schbaurmid, H.; Koth, D. Naturwis-
senschaften 1976, 63, 482. (f) Wilder, H. J .; Hausen, H. D.; Weidlein,
J . Z. Naturforsh. 1975, 30, 645.
(18) Kloo, L. A.; Taylor, M. J . J . Chem. Soc., Dalton Trans. 1997,
2693. (b) Taylor, M. J .; Tuck, D. G. J . Chem. Soc., Dalton Trans. 1981,
928. (c) Abram, S.; Maichle-Mo¨ssmer, C.; Abram, U. Polyhedron 1998,
17, 131.
(19) (a) Hobbs, C. W.; Tobias, R. S. Inorg. Chem. 1970, 9, 1998. (b)
Olapinski, H.; Weidlein, J .; Hausen, H. D. J . Organomet. Chem. 1974,
64, 193. (c) Hausen, H. D.; Schwering, H. U. Z. Anorg. Allg. Chem.
1973, 398, 119. (d) Olapinski, H.; Weidlein, J . J . Organomet. Chem.
1973, 54, 87.
(22) (a) Bent, H. A. J . Chem. Educ. 1960, 37, 616. (b) Bent, H. A.
Chem. Rev. 1961, 61, 275.
(23) The In-Cl and In-Me cone angles are estimated to be 96° and
97°, respectively, so steric effects do not contribute to the difference
in X-In-X angles in 3 and 4.

Cationic Indium Alkyl Complexes
Organometallics, Vol. 21, No. 6, 2002 1169
Sch em e 2
F igu r e 1. Molecular structure of (iPr2-ATI)InCl2 (3).
Hydrogen atoms are omitted.
(74.10° av) and N-In-C angles (110.4° av) in 4 are
correspondingly smaller than the N-In-N (78.46° av)
and N-In-Cl (117.70° av) angles in 3. The core struc-
ture of 4 is similar to that in the oxamidinate complex
Me2In{(MeN)2CC(NMe)2}InMe2, in which the InMe2
units are incorporated into five-membered chelate rings
which are directly analogous to that in 4.24 The In-Cl
distances in 3 (2.350 Å av) are similar to those in
InCl3(NMe3)2 (2.359 Å av)25 and are in the range
normally observed for terminal In-Cl bonds (2.31-2.43
Å).26 The In-Me distances in 4 (2.157 Å av) are similar
to those in Me2In{(MeN)2CC(NMe)2}InMe2 (2.175 Å
i
av)24 and {Me2In(µ-NMePh)}2 (2.153 Å av).27 The Pr2-
F igu r e 2. Molecular structure of (iPr2-ATI)InMe2 (4).
Hydrogen atoms are omitted.
ATI ligand in 4 is slightly twisted such that the angle
between the InN2C2 plane and the seven-membered ring
plane is 6.3° and 13.4° in the two independent mol-
ecules. The twist angle is smaller in 3 (2.7° and 1.4°).
Similar twist distortions were observed in Li, Zr, Hf,
and Y aminotroponiminate compounds.28
Electr op h ilic Ad d ition of CP h 3+ to 4. The reaction
of 4 with 1 equiv of [Ph3C][B(C6F5)4] in pentane (23 °C,
20 h) yields the diimine complex [{1,2-(NiPr)2-5-CPh3-
cyclohepta-3,6-diene}InMe2][B(C6F5)4] (5, Scheme 2),
which is isolated as a pale yellow solid in 90% yield.
F igu r e 3. Molecular structure of the {1,2-(NiPr)2-5-CPh3-
cyclohepta-3,6-diene}InMe2+ cation in 5. Hydrogen atoms
are omitted.
+
Compound 5 forms by electrophilic addition of CPh3
i
1
to C5 of the Pr2-ATI ligand of 4. The H and 13C NMR
spectra for 5 each contain two In-Me resonances, one
iPr-CH resonance, and two iPr-Me2 resonances, consist-
ent with Cs symmetry at In. The 13C NMR resonance
3
t, J HH ) 9.2 Hz). Analogous {1,2-(NiPr)2-5-CPh3-cyclo-
+
hepta-3,6-diene}AlMe2 addition products were ob-
1
for C5 of 5 appears at δ 47.5 with J CH ) 120 Hz,
served as intermediates in the reaction of (iPr2-ATI)AlR2
(R ) Me, Et) with [Ph3C][B(C6F5)4] at low temperature,
but these adducts convert to (iPr2-ATI)AlR+ species at
ca. -40 °C.29
characteristic of sp3 hybridization and indicative of
addition of CPh3+ at this position. For comparison, the
C5 resonance for 4 appears at δ 112.7 (1J CH ) 151),
characteristic of sp2 hybridization. Similarly, the 1H
NMR H5 resonance of 5 (δ 5.35; t, 3J HH ) 6.1) is shifted
upfield from the corresponding resonance of 4 (δ 6.13;
Molecu la r Str u ctu r e of 5. The molecular structure
of 5 was confirmed by X-ray crystallography (Figure 3
and Table 3). Addition of the CPh3 group to the C5
position results in disruption of the π-delocalization and
pronounced bond length alternation within the ATI ring.
The CdNiPr distances (1.286 Å av) are characteristic
of C(sp2)dN double bonds.30 The In-C bond distances
(2.130 Å av) are ca. 0.03 Å shorter than those in 4, while
the In-N distances (2.255 Å av) are ca. 0.07 Å longer
than those in 4 (2.185 Å av), as expected due to
(24) Gerstner, F.; Schwarz, W.; Hausen, H. D.; Weidlein, J . J .
Organomet. Chem. 1979, 175, 33.
(25) Karia, R.; Willey, G. R.; Drew, M. G. B. Acta Crystallogr. C.
1986, 42, 558.
(26) Starowieyski, K. B. In Chemistry of Aluminium, Gallium,
Indium and Thallium; Downs, A. J ., Ed.; Chapman & Hall: London,
UK, 1993; p 335.
(27) Beachley, O. T.; Bueno, C.; Churchill, M. R.; Hallock, R. B.;
Simmons, R. G. Inorg. Chem. 1981, 20, 2423.
(28) (a) Dias, H. V. R.; J in, W.; Ratcliff, R. E. Inorg. Chem. 1996,
35, 6074. (b) Roesky, P. W. Chem. Ber. 1997, 130, 859. (c) Roesky, P.
W. Eur. J . Inorg. Chem. 1998, 593.
(29) Ihara, E.; Korolev, A. V.; J ordan, R. F. Unpublished results.
(30) Levine, I. R. J . Chem. Phys. 1963, 38, 2326.

1170 Organometallics, Vol. 21, No. 6, 2002
Delpech et al.
Ta ble 1. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for 3
in C6D5Cl solution, but rapid solvent exchange results
in time-averaged C2v symmetry.
In(1)-Cl(1)
In(1)-Cl(2)
In(1)-N(1)
In(1)-N(2)
N(1)-C(4)
N(2)-C(10)
2.3447(7)
2.3515(9)
2.093(2)
2.098(2)
1.346(3)
1.342(3)
In(2)-Cl(1′)
In(2)-Cl(2′)
In(2)-N(1′)
In(2)-N(2′)
N(1′)-C(4′)
N(2′)-C(10′)
2.3466(8)
2.3557(7)
2.103(2)
2.107(2)
1.344(3)
1.342(3)
Solid -Sta te Molecu la r Str u ctu r e of 6‚P h Cl. The
molecular structure of 6‚PhCl in the solid state was
determined by X-ray crystallography (Figures 4, 5 and
Table 4). There are two independent cations in the
asymmetric unit. One cation (In(1)) is ion-paired with
-
two B(C6F5)4 anions, while the second cation is com-
Cl(1)-In(1)-Cl(2) 108.99(3) Cl(1′)-In(2)-Cl(2′) 103.56(3)
N(1)-In(1)-N(2) 78.52(8) N(1′)-In(2)-N(2′) 78.39(8)
N(1)-In(1)-Cl(1) 112.81(6) N(1′)-In(2)-Cl(1′) 114.50(6)
N(2)-In(1)-Cl(1) 115.45(6) N(2′)-In(2)-Cl(1′) 120.14(6)
N(1)-In(1)-Cl(2) 123.06(6) N(1′)-In(2)-Cl(2′) 121.75(6)
N(2)-In(1)-Cl(2) 115.45(6) N(2′)-In(2)-Cl(2′) 118.27(6)
plexed with two PhCl molecules and is disordered
between two equally occupied positions (In(2) and In(3)).
The geometry around In(1) (Figure 4) is distorted
trigonal bipyramidal (tbp) with the two axial positions
occupied by the B(C6F5)4- anions (F(20)-In(1)-F(23A)
) 162.3(2)°). The In(1)- F(20) (2.950(5) Å) and In(1)-
F(23A) (2.711(5) Å) distances are intermediate between
the sums of the In and F covalent (2.14 Å) and van der
Waals (vdW) radii (3.37 Å).32 Similar In-F distances
were observed for the intramolecular In- F contacts
involving the ortho-CF3 groups in In2{2,4,6-tris(tri-
fluoromethyl)phenyl)}4 (2.80(1)-2.96(1) Å) and In{2,4,6-
tris(trifluoromethyl)phenyl)}3 (2.722(7)-2.798(5) Å).33
Somewhat longer intermolecular In- F contacts were
observed in In(C6F5)2(κ2-CH2CH2CH2NMe2) (3.175(5)
Å).34
Ta ble 2. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for 4
In(1)-C(1)
In(1)-C(2)
In(1)-N(1)
In(1)-N(2)
N(1)-C(9)
N(2)-C(15)
2.161(2)
2.153(2)
2.187(2)
2.187(2)
1.328(3)
1.334(3)
In(2)-C(1′)
In(2)-C(2′)
In(2)-N(1′)
In(2)-N(2′)
N(1′)-C(9′)
N(2′)-C(15′)
2.156(2)
2.157(2)
2.184(2)
2.184(2)
1.331(3)
1.332(3)
C(1)-In(1)-C(2)
N(1)-In(1)-N(2) 73.78(6)
N(1)-In(1)-C(1)
N(2)-In(1)-C(1)
N(1)-In(1)-C(2)
N(2)-In(1)-C(2)
127.2(1)
C(1′)-In(2)-C(2′)
N(1′)-In(2)-N(2′) 74.42(6)
129.2(1)
109.59(9) N(1′)-In(2)-C(1′)
107.84(8)
113.15(9) N(2′)-In(2)-C(1′)
111.70(8)
111.78(9)
108.58(8)
112.16(8) N(1′)-In(2)-C(2′)
108.43(8) N(2′)-In(2)-C(2′)
The In(2) and In(3) cations of 6‚PhCl are structurally
very similar and feature tbp geometries with PhCl
ligands in the axial positions (Figure 5). The In-Cl
dative bond distances (In(3)-Cl(2) 3.061(4) Å, In(3)-
Cl(3) 3.272(3) Å) are intermediate between the sums of
the In and Cl covalent and vdW radii (2.49 and 3.65
Å)32 and are comparable to the In-µCl distances in
polymeric MeInCl2 (3.20 Å) and {(H2Bpz2)InMe(µ-Cl)}2
Ta ble 3. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for 5
In-C(1)
In-N(1)
N(1)-C(6)
C(6)-C(7)
C(7)-C(8)
C(8)-C(9)
C(9)-C(16)
2.128(2)
2.251(2)
1.287(3)
1.462(3)
1.334(3)
1.483(3)
1.609(2)
In-C(2)
In-N(2)
N(2)-C(12)
C(11)-C(12)
C(10)-C(11)
C(9)-C(10)
2.131(2)
2.260(2)
1.285(3)
1.462(3)
1.333(3)
1.493(3)
-
(H2Bpz2 ) dihydrobis(pyrazolyl)borate; 3.066(1) and
3.203(1) Å).35,36 The structure of the chlorobenzene
ligand is not significantly perturbed by coordination.
The C(200)-Cl(2) (1.702(6) Å) and C(300)-Cl(3) (1.729(5)
Å) distances in 6‚PhCl are close to the C-Cl bond
distance in free chlorobenzene (1.737(5) Å gas phase).37
As illustrated in Figure 5, the two PhCl ligands are
C(1)-In-C(2)
N(1)-In-C(1)
N(1)-In-C(2)
139.0(1)
103.40(9)
109.51(9)
N(1)-In-N(2)
N(2)-In-C(1)
N(2)-In-C(2)
71.84(6)
102.57(9)
110.34(9)
conversion of the formally anionic Pr2-ATI- ligand in
4 to a neutral diimine ligand in 5. The In center in 5
has a highly distorted tetrahedral geometry, with a
large C-In-C angle (139.0(1)°) and small N-In-N
i
i
nearly parallel to the Pr2-ATI plane (angles between
planes 4.4° and 8.8°) and are shifted off-center in
opposite directions, such that the electron-deficient PhCl
ipso carbons are located above and below the electron-
+
angle (71.84(6)°), reflecting the tendency of the InMe2
i
rich Pr2-ATI nitrogens (C(200)-N(2B) 3.35 Å, C(300)-
unit to adopt a more linear geometry as the donor ability
N(1B) 3.51 Å), and the PhCl ring centroids lie above and
of the additional ligands becomes weaker.20,21
i
below the electron-deficient Pr2-ATI iminato carbons
Syn t h esis of [(iP r 2-ATI)In Me][B(C6F 5)4]‚C6H5Cl
(6‚P h Cl). Thermolysis of 5 at 75 °C (12 h, C6H5Cl)
yields a 1:1 mixture of [(iPr2-ATI)InMe][B(C6F5)4] (6)
and Ph3CMe (Scheme 2), presumably by dissociation of
(centroid(200)-C(11B) 3.41 Å, centroid(300)-C(5B) 3.47
Å). This orientation permits an attractive π-stacking
interaction between PhCl and ATI rings.38 Thus it
appears that both dative In-ClPh bonding and π-stack-
ing interactions contribute to the PhCl coordination in
6‚PhCl.
CPh3 to regenerate 4 and CPh3+, followed by Me-
+
abstraction. The chlorobenzene solvate 6.PhCl was
isolated as a yellow solid in 81% yield by generation of
6 in chlorobenzene, removal of the volatiles, and pentane
washing; 6‚PhCl was also isolated in crystalline form
by recrystallization from chlorobenzene/pentane. The 1H
and 13C NMR spectra for 6 in C6D5Cl each contain one
(32) The covalent and van der Waals radii for In (1.50 and 1.90 Å)
were taken from ref 11, and those for F (0.64 and 1.47 Å) and Cl (0.99
and 1.75 Å) were taken from: Kulawiec, R. J .; Crabtree, R. H. Coord.
Chem. Rev. 1990, 99, 89.
(33) Schluter, R. D.; Cowley, A. H.; Atwood, D. A.; J ones, R. A.; Bond,
M. R.; Carrano, C. J . J . Am. Chem. Soc. 1993, 115, 2070.
(34) Schumann, H.; J ust, O.; Seuss, T. D.; Gorlitz, F. H.; Weimann,
R. J . Organomet. Chem. 1994, 466, 5.
(35) Mertz, K.; Schwarz, W.; Zettler, F.; Hausen, H. D. Z. Natur-
forsch. 1975, 30, 159.
(36) Reger, D. L.; Knox, S. J .; Rheingold, A. L.; Haggerty, B. S.
Organometallics 1990, 9, 2581.
i
i
In-Me resonance, one Pr-CH resonance, and one Pr-
Me2 resonance indicative of C2v symmetry. The 13C NMR
1
C5 resonance appears at δ 118.5 (d, J CH ) 154 Hz),
characteristic of sp2 hybridization. The 11B, 13C, and 19F
NMR data for the B(C6F5)4- anion in 6 are characteristic
of the free anion.31 Complex 6 is undoubtedly solvated
(37) Penionzhkevich, N. P.; Sadova, N. I.; Vilkov, L. V. Zh. Struct.
Khim. 1979, 20, 527.
(31) These data are nearly identical to those for [CPh3][B(C6F5)4].
See the Supporting Information.
(38) Hunter, C. A.; Sanders, J . K. M. J . Am. Chem. Soc. 1990, 112,
5525.

Cationic Indium Alkyl Complexes
Organometallics, Vol. 21, No. 6, 2002 1171
Ta ble 4. Selected Bon d Len gth s (Å) a n d An gles (d eg) for 6‚C6H5Cl
In(1)-C(1)
In(1)-N(1)
In(1)-N(2)
N(1)-C(5)
N(2)-C(11)
In(1)-F(20)
In(1)-F(23A)
2.088(5)
2.069(4)
2.070(4)
1.340(6)
1.335(6)
2.950(5)
2.711(5)
In(2)-C(1A)
In(2)-N(1A)
In(2)-N(2A)
N(1A)-C(5A)
N(2A)-C(11A)
In(2)-Cl(1)
2.121(1)
2.100(1)
2.100(1)
1.333(1)
1.333(1)
3.050(4)
3.284(3)
In(3)-C(1B)
In(3)-N(1B)
In(3)-N(2B)
N(1B)-C(5B)
N(2B)-C(11B)
In(3)-Cl(2)
2.121(1)
2.100(1)
2.100(1)
1.333(1)
1.333(1)
3.061(4)
3.272(3)
In(2)-Cl(4)
In(3)-Cl(3)
N(1)-In(1)-N(2)
N(1)-In(1)-C(1)
N(2)-In(1)-C(1)
F(20)-In(1)-F(23A)
79.5(2)
N(1A)-In(2)-N(2A)
N(1A)-In(2)-C(1A)
N(2A)-In(2)-C(1A)
Cl(1)-In(2)-Cl(4)
78.6(2)
N(1B)-In(3)-N(2B)
N(1B)-In(3)-C(1B)
N(2B)-In(3)-C(1B)
Cl(2)-In(3)-Cl(3)
79.2(2)
138.1(2)
142.2(2)
162.3(2)
142.5(3)
138.9(3)
176.6(1)
141.2(3)
139.6(3)
176.4(1)
Sch em e 3
F igu r e 4. Molecular structure of the In(1) site in [(iPr2-
ATI)InMe][B(C6F5)4]‚PhCl (6‚PhCl). Hydrogen atoms are
omitted.
H5 resonance, which appears at δ 6.59 for 7 versus δ
6.70 ppm for 6. These results suggest that MeB(C6F5)3
anion is ion-paired with the cation in 7 in C6D5Cl. The
ion-pairing interaction is labile however, as 7 exhibits
C2v symmetry on the NMR time scale even at 185 K in
CD2Cl2.
-
Compound 7 undergoes ligand redistribution to form
(iPr2-ATI)In(Me)(C6F5) (8) and MeB(C6F5)2 over the
course of 5 h at 23 °C in C6D5Cl (Scheme 3). The
8/MeB(C6F5)2 mixture undergoes further ligand redis-
tribution to yield (iPr2-ATI)In(C6F5)2 (9) and Me2B(C6F5)
-
after 10 days at 23 °C. Analogous C6F5 transfer
processes were observed in the reaction of B(C6F5)3 with
Al and Ga amidinate complexes {tBuC(NR)2}MMe2 and
with {HC(CMeNAr)2}AlMe2 and other Al diketiminate
complexes.8d,40
Molecu la r Str u ctu r e of 9. The molecular structure
of 9 is shown in Figure 6, and selected bond distances
and angles are collected in Table 5. The In-C6F5 bond
distances (2.178(2), 2.164(2) Å) are similar to those in
In(C6F5)2(κ2-CH2CH2CH2NMe2) (2.194(9), 2.196(8) Å)34
and [PPN][In(C6F5)4] (2.189(3)-2.206(3) Å)41 and are
intermediate between the In-C distances in InPh3
(2.11(1), 2.16(1) Å)42 and In{2,4,6-tris(trifluoromethyl)-
phenyl)}3 (2.22 Å av). The C-In-C angle (118.94(8)°)
in 9 is intermediate between the Me-In-Me angle in
4 and the Cl-In-Cl angle in 3.43
F igu r e 5. Molecular structure of the In(3) site in [(iPr2-
ATI)InMe][B(C6F5)4]‚PhCl (6‚PhCl). Hydrogen atoms are
omitted.
Rea ction of 4 w ith B(C6F 5)3. The reaction of 4 with
B(C6F5)3 proceeds by methyl abstraction and yields
[(iPr2-ATI)InMe][MeB(C6F5)3] (7, Scheme 3), which can
be isolated as a yellow solid (77%) by simple filtration
when the reaction is conducted in hexanes. Compound
7 does not react further with excess B(C6F5)3 in C6D5Cl
-
1
(39) The MeB(C6F5)3 anion is considered to be a free anion in
at 23 °C. The H NMR spectrum of 7 (C6D5Cl, 23 °C)
[NBu3(CH2Ph)][MeB(C6F5)3] in C6D5Cl solution. See: Supporting In-
formation.
(40) Baixin, Q.; Ward, D. L.; Smith, M. R. Organometallics 1998,
17, 3070.
(41) Choi, Z.; Tyrra, W.; Adam, A. Z. Anorg. Allg. Chem. 1999, 625,
1287.
(42) Malone, J . F.; McDonald, W. S. J . Chem. Soc. A 1970, 3362.
contains a singlet at δ 1.00 for the MeB(C6F5)3- group,
which is slightly shifted from the free anion resonance
i
(δ 1.11).39 Additionally, the In-Me and Pr2-ATI reso-
nances of 7 are shifted slightly from the corresponding
resonances of 6. This effect is most significant for the

1172 Organometallics, Vol. 21, No. 6, 2002
Delpech et al.
F igu r e 7. Molecular structure of the (iPr2-ATI)In(Me)-
(NMe2Ph)+ cation in 10. Hydrogen atoms are omitted.
F igu r e 6. Molecular structure of (iPr2-ATI)In(C6F5)2 (9).
Hydrogen atoms are omitted.
Ta ble 6. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for 10
In-C(1)
In-N(1)
N(1)-C(5)
2.121(2)
2.112(2)
1.333(3)
In-N(3)
2.405(2)
2.104(2)
1.351(3)
Ta ble 5. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for 9
In-N(2)
N(2)-C(11)
In-C(14)
In-N(1)
N(1)-C(4)
2.178(2)
2.126(2)
1.330(3)
In-C(20)
In-N(2)
N(2)-C(10)
2.164(2)
2.129(2)
1.337(2)
N(1)-In-N(2)
C(1)-In-N(1)
N(1)-In-N(3)
78.18(6)
133.62(9)
103.79(6)
C(1)-In-N(3)
C(1)-In-N(2)
N(2)-In-N(3)
99.79(8)
131.03(9)
107.10(7)
C(14)-In-C(20)
N(1)-In-C(14)
N(1)-In-C(20)
118.94(8)
110.43(7)
118.09(7)
N(1)-In-N(2)
N(2)-In-C(14)
N(2)-In-C(20)
76.59(6)
115.10(7)
110.45(7)
symmetrically displaced from the N-In-N plane.45 The
difference in the coordination geometry of 10 versus 3,
4, and 9 is readily apparent from comparison of Figures
7 and 2. The trigonal distortion in 10 is due to the
difference in the donor ability of the Me and NMe2Ph
ligands. As the donor ability of L in a (iPr2-ATI)E(R)(L)+
species decreases, the (iPr2-ATI)E(R)+ unit approaches
the planar structure expected for the base-free species.8c
This trend was observed previously for (iPr2-ATI)Al-
Rea ction of 4 w ith [HNMe2P h ][B(C6F 5)4]. The
reaction of 4 with 1 equiv of [HNMe2Ph][B(C6F5)4] in
C6D5Cl (23 °C) generates the amine adduct [(iPr2-
ATI)In(Me)(NMe2Ph)][B(C6F5)4] (10) and methane (eq
1
1). The H and 13C NMR spectra of 10 contain NMe2Ph
resonances which are shifted from those of free NMe2Ph,
consistent with coordination of the amine to In.44
However, 10 exhibits Cs symmetry on the NMR time
scale at 23 °C and at low temperature (185 K in CD2Cl2),
which indicates that intermolecular amine exchange is
fast.
i
(R)(L)+ cations.10 The Pr2-ATI ligand in 10 is slightly
twisted such that the dihedral angle between the InN2C2
and the seven-membered ring planes is 11.2°. The In-
N(amine) bond distance (2.405(2) Å) is in the range
observed for other four-coordinate In(III) amine com-
plexes (2.29-2.50 Å).46
Rea ctivity of (iP r 2-ATI)In (Me)+. The addition of 1
equiv of the appropriate Lewis base to 6 in C6D5Cl yields
the adducts [(iPr2-ATI)In(Me)(L)][B(C6F5)4] (L ) NMe2Ph
(10), CH3CN (11), Me2CO (12), and PMe3 (13, eq 2).
Similarly, 7 reacts with Lewis bases to yield [(iPr2-ATI)-
In(Me)(L)][MeB(C6F5)3] adducts (L ) NMe2Ph (14),
PMe3 (15), eq 2). The NMR spectra of these adducts
contain resonances for the coordinated Lewis base that
are shifted from the free base resonances.44 How-
ever, in each case the NMR spectra show that the (iPr2-
ATI)In(Me)(L)+ cation has time-averaged C2v sym-
Molecu la r Str u ctu r e of 10. Compound 10 crystal-
lizes as discrete ions, and the structure of the B(C6F5)4
-
anion is normal. The structure of the cation of 10 is
illustrated in Figure 7, and selected bond distances and
angles are collected in Table 6. The geometry at In is
distorted trigonal pyramidal, and the NMe2Ph ligand
occupies the apical site. Thus the In-Me and In-
NMe2Ph groups are displaced from the NATI-In-NATI
plane by 29.2° and 69.8°, respectively. In contrast, in
each of the (iPr2-ATI)InX2 compounds 3 (X ) Cl), 4 (X
) Me), and 9 (X ) C6F5), the two X ligands are
(45) Displacements of X groups from N-In-N plane (deg) are as
follows. 3: molecule 1: 58.07, 50.48; molecule 2: 53.45, 49.74; 4:
molecule 1: 62.80, 64.12, molecule 2: 64.0.68, 64.19; 9: 60.26, 57.87.
(46) (a) Atwood, D. A.; Coley, A. H.; J ones, R. A.; Atwood, J . L.; Bott,
S. G. J . Coord. Chem. 1992, 26, 293. (b) Bradley, D. C.; Dawes, H.;
Frigo, D. M.; Hursthouse, M. B.; Hussain, B. J . Organomet. Chem.
1987, 325, 55. (c) Schumann, H.; Hartmann, U.; Wassermann, W.;
Dietrich, A.; Gorlitz, F. H.; Pohl, L.; Hostalek, M. Chem. Ber. 1990,
123, 2093. (d) Fisher, R. A.; Nlate, S.; Hoffmann, H.; Herdtweck, E.;
Blumel, J . Organometallics 1996, 15, 5746. (e) Kummel, C.; Meller,
A.; Noltemeyer, M. Z. Naturforsh. 1996, 51, 209. (f) J utzi, P.; Dalhaus,
J .; Neumann, B.; Stammler, H. G. Organometallics 1996, 15, 747. (g)
Atwood, D. A.; J ones, R. A.; Coley, A. H.; Bott, S. G.; Atwood, J . L. J .
Organomet. Chem. 1992, 434, 143.
(43) The In-C6F5 cone angle (145.2°) is significantly larger than the
In-Me or In-Cl cone angles.
(44) See Supporting Information.

Cationic Indium Alkyl Complexes
Organometallics, Vol. 21, No. 6, 2002 1173
metry at 23 °C, consistent with fast intermolecular
exchange of the Lewis base. Low-temperature NMR
spectra of 14 and 15 in CD2Cl2 show that ligand
exchange is fast down to 185 K. The MeB(C6F5)3- salts
14 and 15 are stable in C6D5Cl at 23 °C, which contrasts
with the low stability of 7 under these conditions.
Evidently the Lewis base prevents the reaction of the
cation with the anion. Exposure of 14 to air results in
hydrolysis of the anion and formation of (iPr2-ATI)In-
(Me)(µ-OH)B(C6F5)3.47
Exp er im en ta l Section
Gen er a l P r oced u r es. All operations were carried out
under an atmosphere of purified N2 or under vacuum using a
glovebox or a high-vacuum line. Trimethylindium was pur-
chased from Strem and used as received. [CPh3][B(C6F5)4],
[NMe2Ph][B(C6F5)4], and B(C6F5)3 were obtained from Boulder
Scientific and used as received. Other chemicals were pur-
chased from Aldrich and used as received. Solvents were
distilled from Na/benzophenone, except for CH2Cl2, which was
distilled from CaH2. Methylene chloride-d2, chlorobenzene-d5,
and benzene-d6 (Cambridge) were dried over CaH2 for 24 h
and degassed by freeze-pump-thaw cycles.
1H, 13C, 11B, and 31P NMR spectra were recorded on a Bruker
AMX-360 spectrometer, and 19F NMR spectra were recorded
on a Bruker AC-300 spectrometer in flamed-sealed or Teflon-
valved tubes at ambient probe temperature unless otherwise
indicated. 1H and 13C chemical shifts are reported versus SiMe4
and were determined by reference to the residual solvent
peaks. 11B chemical shifts are reported versus BF3‚Et2O (0.1
M in C6D5Cl), 19F chemical shifts are reported versus CFCl3
in CDCl3, and 31P chemical shifts are reported versus H3PO4
(85% in THF-d8). Coupling constants are reported in Hz.
Elemental analyses were performed by Midwest Microlabs,
Indianapolis, IN.
Li[iP r 2-ATI] (2). A solution of (iPr2-ATI)H (1.10 g, 5.35
mmol) in Et2O (25 mL) was cooled to 0 °C. BuLi (3.3 mL of a
Compound 6 does not react with ethylene (1 atm, 70
°C), tBuCtCH (80 °C), H2 (1 atm, 23 °C), or CO (1 atm,
23 °C) and shows only trace activity for isobutylene
polymerization.
n
1.6 M solution in hexanes, 5.35 mmol) was added dropwise.
The mixture was allowed to warm to room temperature and
was stirred for 2 h. The volatiles were removed under vacuum,
yielding an orange solid, which was washed with pentane and
1
dried under vacuum (1.08 g, 95%). H NMR (C6D6): δ 1.19 (d,
Con clu sion
3J HH ) 6.1, 12H, Me), 3.95 (sept, 3J HH ) 6.1, 2H, CHMe2), 6.24
3
3
(t, J HH ) 9.0, 1H, H5), 6.57 (d, J HH ) 11.2, 2H, H3,7), 7.05 (t,
The reaction of (iPr2-ATI)InMe2 (4) with [CPh3]-
[B(C6F5)4] yields the cationic complex [(iPr2-ATI)InMe]-
[B(C6F5)4] (6), which is isolated as the PhCl solvate
6‚PhCl. Two independent (iPr2-ATI)InMe+ cations are
present in the solid-state structure of 6‚PhCl: one cation
3J HH ) 9.7, 2H, H4,6).
(iP r 2-ATI)In Cl2 (3). A solution of Li[iPr2-ATI] (5.10 mmol)
in Et2O (25 mL) was generated as described above and cooled
to -78 °C. A solution of InCl3 (1.13 g, 5.10 mmol) in THF (50
mL) was added dropwise at -78 °C. The mixture was allowed
to warm to room temperature and was stirred overnight. The
volatiles were removed under vacuum, and the crude product
was extracted with toluene. The extract was filtered and
concentrated, and pentane was added, resulting in the pre-
cipitation of a pale yellow solid, which was isolated by filtration
-
(In(1)) which is ion-paired with two B(C6F5)4 anions
via In-F contacts and a second disordered cation (In(2)
and In(3)) which is complexed by two PhCl ligands by
dative In-ClPh bonding and PhCl/ATI π-stacking
interactions. Compound
4
reacts with B(C6F5)3
1
3
to yield [(iPr2-ATI)InMe][MeB(C6F5)3], which decom-
(1.27 g, 64%). H NMR (CD2Cl2): δ 1.46 (d, J HH ) 6.1, 12H,
3
3
CHMe2), 4.19 (sept, J HH ) 6.1, 2H, CHMe2), 6.70 (t, J HH
)
)
)
-
poses at 23 °C by C6F5 transfer processes and with
9.2, 1H, H5), 6.93 (d, J HH )11.5, 2H, H3,7), 7.32 (dd, J HH
3
3
[NMe2Ph][B(C6F5)4] to yield the labile amine complex
[(iPr2-ATI)In(Me)(NMe2Ph)][B(C6F5)4] (10). Thus [CPh3]-
[B(C6F5)4] is the most useful reagent for generating
(iPr2-ATI)InR+ species. Several observations suggest
that (iPr2-ATI)InR+ cations will be less reactive than
the corresponding (iPr2-ATI)AlR+ species studied ear-
lier.10 Most notably (i) while the reaction of (iPr2-ATI)-
AlMe2 with 1 equiv of Ph3C+ yields {(iPr2-ATI)Al(Me)}2-
(µ-Me)+ (and 0.5 equiv of unreacted Ph3C+) via trapping
of the initial product (iPr2-ATI)Al(Me)+ by (iPr2-ATI)-
AlMe2, the analogous dinuclear In cation is not observed
in the reaction of 4 with Ph3C+, (ii) (iPr2-ATI)AlR+
cations catalyze the dimerization of terminal alkynes
by an insertion/σ-bond metathesis mechanism, whereas
9.4 and 11.5, 2H, H4,6). 13C NMR (CD2Cl2): δ 24.4 (q, J CH
1
1
1
127, Me), 48.9 (d, J CH ) 137, CHMe2), 116.4 (d, J CH ) 153,
C5), 122.6 (d, 1J CH ) 161, C3,7), 136.9 (d, 1J CH ) 145, C4,6), 158.0
(s, C1,2). Anal. Calcd for C13H19Cl2InN2: C, 40.13; H, 4.92;
N,7.20. Found: C, 40.15; H, 4.85; N, 7.14.
(iP r 2-ATI)In Me2 (4). A solution of (iPr2-ATI)H (0.758 g, 3.71
mmol) in pentane (20 mL) was added to a solution of InMe3
(0.630 g, 3.94 mmol) in pentane (20 mL). The mixture was
stirred for 30 min, concentrated to 20 mL, and cooled to -78
°C for 22 h, resulting in the formation of a yellow crystalline
solid, which was isolated by filtration (1.19 g, 92%). Alternate
synthesis: Excess MeLi (0.4 mL of a 1.4 M solution in Et2O,
0.56 mmol) was added to a solution of (iPr2-ATI)InCl2 (0.074
g, 0.19 mmol) in Et2O at -78 °C. The mixture was warmed to
room temperature and stirred overnight. The volatiles were
removed under vacuum, and the product was extracted from
the LiCl with pentane. The pentane extract was concentrated
and cooled to -78 °C to afford (iPr2-ATI)InMe2 as yellow
t
(iPr2-ATI)InMe+ does not react with BuCtCH, and (iii)
(iPr2-ATI)AlR+ species initiate the polymerization of
isobutylene, while (iPr2-ATI)InMe+ shows only trace
activity with this substrate. These differences reflect the
lower Lewis acidity and the lower E-C bond polarity
in the In complexes compared to the Al complexes.
1
crystals, which were isolated by filtration (0.058 g, 88%). H
NMR (CD2Cl2): δ -0.20 (s, 6H, InMe), 1.25 (d, 3J HH ) 6.3, 12H,
3
3
CHMe2), 3.96 (sept, J HH ) 6.3, 2H, CHMe2), 6.13 (t, J HH
)
)
9.2, 1H, H5), 6.41 (d, J HH ) 11.9, 2H, H3,7), 6.90 (dd, J HH
3
3
9.0 and 11.9, 2H, H4,6). 1H NMR (C6D5Cl): δ -0.06 (s, 6H,
(47) Guzei, I. A.; Delpech, F.; J ordan, R. F. Acta Crystallogr., Sect.
C: Cryst. Struct. Commun. 2000, C56, E327.
3
3
InMe), 1.09 (d, J HH ) 6.3, 12H, CHMe2), 3.70 (sept, J HH
)

1174 Organometallics, Vol. 21, No. 6, 2002
Delpech et al.
3
3
3
6.3, 2H, CHMe2), 6.17 (t, J HH ) 9.2, 1H, H5), 6.27 (d, J HH
)
(C6D5Cl): δ -132.3 (m, 6F, o-C6F5), -163.6 (t, J FF ) 20, 3F,
3
11.9, 2H, H3,7), 6.84 (dd, J HH ) 9.0 and 11.9, 2H, H4,6). 13C
p-C6F5), -166.4 (m, 6F, m-C6F5). Anal. Calcd for C33H25BF15-
InN2: C, 46.08; H, 2.93; N, 3.26. Found: C, 45.99; H, 2.99; N,
1
1
NMR (CD2Cl2): δ -4.1 (q, J CH ) 126, InMe2), 23.8 (q, J CH
)
)
1
1
128, CHMe2), 48.7 (d, J CH ) 135, CHMe2), 112.7 (d, J CH
3.24.
151, C5), 116.3 (d, J CH ) 161, C3,7) 135.3 (d, J CH ) 155, C4,6),
161.0 (s, C1,2). 13C NMR (C6D5Cl): δ -3.9 (InMe), 23.8 (CHMe2),
48.7 (CHMe2), 112.5 (C5), 116.3 (C3,7), 135.3 (C4,6), 160.8 (C1,2).
1
1
Rea ction of (iP r 2-ATI)In (Me)+ w ith MeB(C6F 5)3-. An
NMR tube was charged with [(iPr2-ATI)In(Me)][MeB(C6F5)3]
(0.025 g, 0.029 mmol), and C6D5Cl (0.5 mL) was added by
vacuum transfer at -78 °C. The tube was maintained at 23
°C and monitored by 1H NMR. The NMR spectra showed that
complete conversion of the starting material to (iPr2-ATI)In-
(C6F5)(Me) (8) and MeB(C6F5)2 had occurred after 5 h and
complete conversion to (iPr2-ATI)In(C6F5)2 (9) and MeB(C6F5)2
Anal. Calcd for
C15H25InN2: C, 51.74; H, 7.24; N, 8.05.
Found: C, 51.54; H, 7.13; N, 8.15.
[{1,2-(N i P r )2-5-C P h 3-c y c lo h e p t a -3,6-d ie n e }I n Me 2]-
[B(C6F 5)4] (5). A mixture of (iPr2-ATI)InMe2 (0.158 g, 0.453
mmol) and [CPh3][B(C6F5)4] (0.418 g, 0.453 mmol) in hexanes
(5 mL) was stirred at 23 °C for 3 days, resulting in the
formation of a yellow solid. The mixture was filtered, and the
solid was washed with hexanes (3 × 5 mL) and dried under
vacuum to afford a yellow solid (0.516 g, 90%). 1H NMR
(C6D5Cl): δ -0.08 (s, 3H, InMe), 0.00 (s, 3H, InMe), 0.90 (d,
had occurred after 10 days. Data for (iPr2-ATI)In(C6F5)(Me)
(8). 1H NMR (C6D5Cl): δ 0.33 (s, 3H, InMe), 1.01 (d, J HH
3
)
3
6.5, 6H, CHMe), 1.09 (d, J HH ) 6.5, 6H, CHMe), 3.72 (sept,
3J HH ) 6.5, 2H, CHMe2), 6.29 (t, J HH ) 9.2, 1H, H5), 6.42 (d,
3
3J HH ) 11.9, 2H, H3,7), 6.93 (dd, 3J HH ) 9.4 and 11.9, 2H, H4,6).
3
3J HH ) 4.0, 6H, CHMe), 0.92 (d, J HH ) 4.0, 6H, CHMe), 3.42
13C NMR (C6D5Cl): δ -3.8 (q, 1J CH ) 128, InMe), 23.4 (q, 1J CH
3
3
(m, 2H, CHMe2), 5.35 (t, J HH ) 6.1,1H, H5), 5.81 (d, J HH
)
1
1
) 127, CHMe), 24.1 (q, J CH ) 128, CHMe), 48.1 (d, J CH
)
3
13.0, 2H, H3,7), 6.72 (dd, J HH ) 6.1 and 12.6, 2H, H4,6), 7.06
135, CHMe2), 114.0 (d, J CH ) 151, C5), 118.4 (d, J CH ) 160,
1
1
(br m, 15H, CPh3). 13C NMR (C6D5Cl): δ -2.9 (q, J CH )132,
1
C3,7), 121.2 (br t, ipso-C6F5, J CF ) 60), 135.8 (d, J CH ) 156,
2
1
InMe), -2.1 (q, 1J CH ) 133, InMe), 22.8 (q, 1J CH ) 126, CHMe),
C4,6), 137.0 (d, 1J CF ) 254, o-C6F5), 141.2 (d, 1J CF ) 255, p-C6F5),
23.7 (q, J CH ) 129, CHMe), 47.5 (d, J CH ) 120, C5) 52.8 (d,
1
1
149.0 (d, J CF ) 231, m-C6F5), 160.5 (s, C1,2). 19F NMR
1
1J CH ) 141 CHMe2), 64.8 (s, CPh3), 121.4 (d, 1J CH ) 162, C3,7),
3
(C6D5Cl): δ -118.3 (m, 2F, o-C6F5), -154.3 (t, J FF ) 20, 1F,
1
1
125 (br, ipso-C6F5), 136.9 (d, J CF ) 243, C6F5), 138.7 (d, J CF
p-C6F5), -160.5 (m, 2F, m-C6F5). Data for MeB(C6F5)2. 1H NMR
) 245, C6F5), 148.5 (d, J CH ) 160, C4,6), 148.9 (d, J CF ) 241,
1
1
(C6D5Cl): δ 1.53 (quintet, J HF ) 1.8, 3H). 13C NMR (C6D5Cl):
5
C6F5), 161.5 (s, C1,2); the remaining Ph resonances are broad
1
1
δ 15.3 (s, br, MeB), 137.5 (d, J CF ) 254, C6F5), 143.8 (d, J CF
due to restricted rotation. 11B NMR (C6D5Cl): δ -16.5 (s). 19F
1
) 247, C6F5), 147.8 (d, J CF ) 249, C6F5); the ipso-C6F5
3
NMR (C6D5Cl): δ -132.0 (m, 8F, o-C6F5), -162.6 (t, J FF
20, 4F, p-C6F5), -166.5 (m, 8F, m-C6F5). Anal. Calcd for C58H40
BF20InN2: C, 54.83; H, 3.17; N, 2.21. Found: C, 53.84; H, 3.12;
N, 2.28.
)
-
resonance was not observed. 11B NMR (C6D5Cl): δ 71.5 (br s).
19F NMR (C6D5Cl): δ -129.3 (m, 4F, o-C6F5), -147.1 (m, 2F,
p-C6F5), -161.1 (m, 4F, m-C6F5). Data for (iPr2-ATI)In(C6F5)2
(9). 1H NMR (C6D5Cl): δ 1.11 (d, J HH ) 6.1, 12H, CHMe2),
3
[(iP r 2-ATI)In Me][B(C6F 5)4]‚C6H5Cl (6‚C6H5Cl). A solution
of [{1,2-(NiPr)2-5-CPh3-cyclohepta-3,6-diene}InMe2][B(C6F5)4]
(0.148 g, 0.130 mmol) in C6H5Cl (10 mL) was heated to 75 °C
for 12 h. The volatiles were removed under vacuum, leaving
an oily dark yellow residue. Trituration with pentane afforded
pure [(iPr2-ATI)InMe][B(C6F5)4]‚C6H5Cl as a yellow solid (0.104
mg, 79%). 1H NMR (C6D5Cl): δ 0.70 (s, 3H, InMe), 1.04 (d,
3J HH ) 6.1, 12H, CHMe2), 3.65 (sept, 3J HH ) 6.1, 2H, CHMe2),
3
3
3.77 (sept, J HH ) 6.1, 2H, CHMe2), 6.38 (t, J HH ) 11.0, 1H,
H5), 6.54 (d, J HH ) 14.4, 2H, H3,7), 6.98 (dd, J HH ) 11.2 and
3
3
14.4, 2H, H4,6). 13C NMR (C6D5Cl): δ 23.5 (q, J CH ) 129,
1
1
1
CHMe2), 48.9 (d, J CH ) 139, CHMe2), 115.4 (d, J CH ) 151,
C5), 117.6 (t, br, J CF ) 55, ipso-C6F5), 120.3 (d, J CH ) 162,
2
1
C3,7), 136.3 (d, J CH ) 153, C4,6), 139.6 (d, J CF ) 255, o -C6F5),
1
1
1
1
141.9 (d, J CF ) 252, p-C6F5), 147.6 (d, J CF ) 234, m-C6F5),
160.2 (s, C1,2). 19F NMR (C6D5Cl): δ -117.8 (m, 4F, o-C6F5),
-152.1 (t, 3J FF ) 20, 2F, p-C6F5), -159.7 (m, 4F, m-C6F5). Data
6.69 (d, J HH ) 11.9, 2H, H3,7), 6.70 (t, J HH ) 8.6, 1H, H5),
3
3
7.15 (m, 2H, H4,6). 13C NMR (C6D5Cl): δ 2.6 (q, J CH ) 138,
1
1
for Me2B(C6F5). H NMR (C6D5Cl): δ 1.09 (s, 3H, overlapped
1
1
InMe), 24.6 (q, J CH ) 128, CHMe2), 48.8 (d, J CH ) 141,
with CHMe2 resonance of 9). 13C NMR (C6D5Cl): δ 16.7 (br s,
CHMe2), 118.5 (d, J CH ) 154, C5), 126.8 (d, J CH ) 156, C3,7),
1
1
1
1
MeB) 141.9 (d, J CF ) 252, C6F5), 148.9 (d, J CF ) 238, C6F5);
the meta and ipso-C6F5 resonances are obscured. 11B NMR
(C6D5Cl): δ 80.6 (br s). 19F NMR (C6D5Cl): δ -130.3 (m, 2F,
o-C6F5), -151.2 (m, 1F, p-C6F5), -162.4 (m, 2F, m-C6F5).
[(iP r 2-ATI)In (Me)(NMe2P h )][B(C6F 5)4] (10). An NMR
tube was charged with (iPr2-ATI)InMe2 (0.029 g, 0.083 mmol)
and [NMe2Ph][B(C6F5)4] (0.066 g, 0.083 mmol), and C6D5Cl (0.5
mL) was added by vacuum transfer at -78 °C. The tube was
warmed to room temperature, and NMR spectra were recorded
which showed the formation of [(iPr2-ATI)In(Me)(NMe2Ph)]-
137.0 (d, J CF ) 243, C6F5), 137.3 (d, J CH ) 157, C4,6), 138.8
(d, 1J CF ) 245, C6F5), 149.0 (d, 1J CF ) 241, C6F5), 158.3 (s, C1,2);
the ipso-C6F5 resonance was not observed. 11B NMR (C6D5Cl):
δ -16.5 (s). 19F NMR (C6D5Cl): δ -132.0 (m, 8F, o-C6F5),
-162.6 (t, 3J FF ) 21, 4F, p-C6F5), -166.4 (m, 8F, m-C6F5). Anal.
Calcd for C38H22BF20InN2‚C6H5Cl: C, 46.99; H, 2.42; N, 2.49.
Found: C, 46.61; H, 2.23; N, 2.64.
1
1
[(iP r 2-ATI)In Me][MeB(C6F 5)3] (7). A mixture of (iPr2-ATI)-
InMe2 (0.199 g, 0.572 mmol) and B(C6F5)3 (0.293 g, 0.572 mmol)
in hexanes (5 mL) was stirred at 23 °C for 2 h, resulting in
the formation of a yellow solid. The solid was collected by
filtration, washed with hexanes (3 × 5 mL), and dried under
vacuum to afford pure [(iPr2-ATI)InMe][MeB(C6F5)3] as a
1
[B(C6F5)4] (10, 85%). H NMR (C6D5Cl): δ 0.40 (s, 3H, InMe),
0.81 (d, 3J HH ) 6.1, 12H, CHMe2), 2.35 (s, 6H, NMe2), 3.51 (sept,
3J HH ) 6.1, 2H, CHMe2), 6.59-6.64 (m, 5H, H3,7 and H5
3
1
overlapped with NMe2Ph), 6.94 (t, 1H, J HH ) 7.9, Ph), 7.10
yellow solid (0.378 g, 77%). H NMR (C6D5Cl): δ 0.62 (s, 3H,
(m, 4H, H4,6 overlapped with NMe2Ph). H NMR (CD2Cl2): δ
1
InMe), 1.00 (br s, 3H, MeB), 1.04 (d, 3J HH ) 6.1, 12H, CHMe2),
3
3
0.73 (br s, 3H, InMe), 1.01 (br s, 12H, CHMe2), 2.77 (s, 6H,
3.67 (sept, J HH ) 6.1, 2H, CHMe2), 6.59 (t, J HH ) 9.7, 1H,
NMe2), 3.89 (br s, 2H, CHMe2), 6.83 (br s, 1H, H5), 6.98 (d,
H5), 6.64 (d, J HH ) 11.5, 2H, H3,7), 7.10 (t, J HH) 10.3, 2H,
3
3
3J HH ) 11.6, 2H, H3,7), 7.09 (d, J HH ) 7.6, 2H, Ph), 7.26 (t,
3
H4,6). H NMR (CD2Cl2, 195 K): δ 0.36 (br s, 3H, MeB), 1.11
1
1H, J HH ) 7.0, Ph), 7.39 (m, 4H, H4,6 overlapped with
3
(br s, 3H, InMe), 1.36 (br s, 12H, CHMe2), 4.22 (br s, 2H,
CHMe2), 7.00 (t, 3J HH ) 9.6, 1H, H5), 7.16 (d, 3J HH ) 11.0, 2H,
H3,7), 7.52 (t, 3J HH) 9.9, 2H, H4,6). 13C NMR (C6D5Cl): δ 3.1 (q,
NMe2Ph). 13C NMR (C6D5Cl): δ -2.9 (q, J CH ) 135, InMe),
1
1
1
24.9 (q, J CH ) 127, CHMe2), 44.9 (q, J CH ) 139, NMe2), 48.7
1
1
1J CH ) 137, InMe), 12.6 (br s, MeB), 24.5 (q, J CH ) 127,
1
(d, J CH ) 137, CHMe2), 117.6 (d, J CH ) 156, Ph), 118.2 (d,
1J CH ) 152, C5), 124.1 (d, J CH ) 163, C3,7), 125.6 (d, J CH
)
1
1
1
1
CHMe2), 48.8 (d, J CH ) 142, CHMe2), 118.4 (d, J CH ) 153,
162, Ph, 130.2 (d, 1J CH ) 161, Ph), 136.9 (d, 1J CF ) 243, C6F5),
C5), 126.4 (d, J CH ) 155, C3,7), 137.1 (d, J CF ) 246, C6F5),
1
1
136.9 (d, J CH ) 156, C4,6), 138.7 (d, J CF ) 245, C6F5), 147.8
(s, ipso-Ph), 148.9 (d, 1J CF ) 241, C6F5), 160.1 (s, C1,2); the ipso-
C6F5 resonance was not observed. 11B NMR (C6D5Cl): δ -16.5
1
1
137.1 (d, J CH ) 156, C4,6), 138.1 (d, J CF ) 245, C6F5), 149.0
1
1
(d, J CF ) 240, C6F5), 160.8 (s, C1,2); the ipso-C6F5 resonance
1
was not observed. 11B NMR (C6D5Cl): δ -14.6 (s). 9F NMR

Cationic Indium Alkyl Complexes
Organometallics, Vol. 21, No. 6, 2002 1175
Ta ble 7. Su m m a r y of Cr ysta l Da ta for Com p ou n d s 3, 4, 5, 6‚C6H5Cl, 9, a n d 10
3
4
5
6‚C6H5Cl
C44H27BClF20InN2 C25H19F10InN2
1124.76 652.24
9
10
formula
fw
C
13H19Cl2InN2
C15H25InN2
348.19
C58H40BF20InN2
1270.55
C46H33BF20InN3
1133.38
389.02
cryst size (mm)
d(calc), Mg/m3
cryst syst
space group
a (Å)
b (Å)
c (Å)
R (deg)
â (deg)
0.45 × 0.42 × 0.31 0.46 × 0.25 × 0.15 0.40 × 0.35 × 0.35 0.20 × 0.15 × 0.10 0.45 × 0.43 × 0.27
0.41 × 0.39 × 0.39
1.617
1.429
1.625
1.745
1.745
1.683
monoclinic
P21/c
orthorhombic
Pbca
triclinic
P1h
monoclinic
P21/c
orthorhombic
Pna21
monoclinic
P21/c
12.1883(9)
20.925(2)
13.8228(1)
16.594(1)
15.534(1)
20.796(1)
9.2365(5)
33.711(2)
11.3595(6)
14.2584(7)
17.0182(8)
89.939(1)
88.532(1)
70.431(1)
2596.3(2)
2
17.4035(9)
10.8193(6)
45.479(2)
16.330(1)
17.700(1)
8.5897(5)
17.570(1)
116.231(1)
90.708(1)
93.187(1)
γ (deg)
V (Å3)
3195.9(4)
8
6475.1(6)
16
8562.7(8)
8
2482.7(3)
4
4473.9(6)
4
Z
T (K)
183(2)
183(2)
183(2)
183(2)
173(2)
183(2)
diffractometer
radiation, λ (Å)
θ range (deg)
data collected: h;k;l
no. of reflns collected
no. of indpt reflns
Rint
Bruker CCD-1000 Bruker CCD-1000 Bruker CCD-1000 Bruker CCD-1000 Bruker CCD-1000
Bruker CCD-1000
Mo KR, 0.710 73
1.95 < θ < 26.37
Mo KR, 0.710 73
1.64 < θ < 26.37
-17,15; 0,20; 0,19 0,25; 0,11; 0,42
Mo KR, 0.710 73
1.21 < θ < 26.37
Mo KR, 0.710 73
1.52 < θ < 26.37
-13,14; (17; 0,21 (21; 0,13; 0,56
Mo KR, 0.710 73
1.46 < θ < 26.37
Mo KR, 0.710 73
1.70 < θ < 26.37
-19,20; -13,26; (10 (15; 0,26; 0,21
18 844
6472
0.0230
1.799
44 343
6623
0.0372
1.447
14 924
9641
0.0119
0.570
56 135
17295
0.0803
0.739
11 469
4577
0.0176
1.045
33 129
9111
0.0162
0.650
µ (mm-1
)
max/min transmn
structure solution
no. of data/retrains/
params
0.6055 and 0.4982 0.8122 and 0.5557 0.8255 and 0.8041 0.9298 and 0.8663 0.7657 and 0.6507
0.7855 and 0.7763
direct methodsa
9111/24/670
direct methodsa
6472/0/333
direct methodsa
6623/0/337
direct methodsa
9641/0/745
direct methodsa
17295/55/1194
direct methodsa
4577/1/347
GOF on F2
1.020
1.021
1.017
0.984
0.988
1.024
R indices (I > 2σ(I))b
R1 ) 0.0260,
wR2 ) 0.0517
R1 ) 0.0412,
wR2 ) 0.0550
R1 ) 0.0224,
wR2 ) 0.0436
R1 ) 0.0414,
wR2 ) 0.0470
0.305
R1 ) 0.0280,
wR2 ) 0.0729
R1 ) 0.0358,
wR2 ) 0.0765
0.393
R1 ) 0.0600,
wR2 ) 0.1081
R1 ) 0.1303,
wR2 ) 0.1275
0.790
R1 ) 0.0169,
wR2 ) 0.0376
R1 ) 0.0199,
wR2 ) 0.0384
0.242
R1 ) 0.0253,
wR2 ) 0.0622
R1 ) 0.0341,
wR2 ) 0.0665
0.739
R indices (all data)b
max diff peak/hole (e/Å3) 0.598
-0.498
-0.302
-0.356
-0.633
-0.357
-0.762
a
b
2
SHELXTL-Version 5.1; Bruker Analytical X-ray systems, Madison, WI. R1 ) ∑||Fo| - |Fc||/∑|Fo| and wR2 ) [∑[w(Fo
-
Fc2)2]/∑[w(Fo2)2]]1/2, where w ) [σ2(Fo2) + (aP)2 + bP]-1
.
(s). 19F NMR (C6D5Cl): δ -132.0 (m, 8F, o-C6F5), -162.7 (t,
3J FF ) 20, 4F, p-C6F5), -166.5 (m, 8F, m-C6F5).
C6F5 resonance was not observed. 11B NMR (C6D5Cl): δ -16.5
(s). 19F NMR (C6D5Cl): δ -132.0 (m, 8F, o-C6F5), -162.7 (t,
3J FF ) 20, 4F, p-C6F5), -166.5 (m, 8F, m-C6F5).
Rea ction of [(iP r 2-ATI)In Me][B(C6F 5)4]‚C6H5Cl (6‚P h Cl)
or [(iP r 2-ATI)In Me][MeB(C6F 5)3] (7) w it h Lew is Ba ses.
Solutions of 6‚PhCl or 7 and 1 equiv of the appropriate Lewis
base were prepared and warmed to room temperature, and
NMR spectra were recorded. In all cases reactions were
complete within the time required to obtain NMR spectra
(minutes). Data for 10 are given above; data for other cases
are listed below.
[(iP r 2-ATI)In (Me)(P Me3)][B(C6F 5)4] (13). 1H NMR
(C6D5Cl): δ 0.25 (s, 3H, InMe), 0.89 (d, 3J HH ) 7.9, 9H, PMe3),
3
3
0.94 (d, J HH ) 6.1, 12H, CHMe2), 3.63 (sept, J HH ) 6.1, 2H,
CHMe2), 6.47 (t, 3J HH ) 9.6, 1H, H5), 6.51 (d, 3J HH ) 11.3, 2H,
H3,7), 7.03 (m, H4,6). 13C NMR (C6D5Cl): δ -4.2 (q, 1J CH ) 132,
InMe), 10.1 (q, 1J CH ) 125, PMe3), 24.4 (q, 1J CH ) 126, CHMe2),
1
1
48.2 (d, J CH ) 133, CHMe2), 116.7 (d, J CH ) 152, C5), 122.9
(d, 1J CH ) 161, C3,7), 136.9 (d, 1J CF ) 243, C6F5), 137.0 (d, 1J CH
[(iP r 2-ATI)In (Me)(MeCN)][B(C6F 5)4] (11). 1H NMR
1
1
3
) 155, C4,6), 138.7 (d, J CF ) 245, C6F5), 148.9 (d, J CF ) 241,
C6F5), 161.3 (s, C1,2); the ipso-C6F5 resonance was not observed.
11B NMR (C6D5Cl): δ -16.5 (s). 19F NMR (C6D5Cl): δ -132.0
(C6D5Cl): δ 0.50 (s, 3H, InMe), 1.10 (d, J HH ) 6.1, 12H,
3
CHMe2), 1.37 (br s, 3H, MeCN), 3.74 (sept, J HH ) 6.1, 2H,
CHMe2), 6.54 (t, 3J HH ) 9.0, 1H, H5), 6.65 (d, 3J HH ) 11.4, 2H,
3
1
(m, 8F, o-C6F5), -162.5 (t, J FF ) 20, 4F, p-C6F5), -166.4 (m,
H3,7), 7.09 (m, 2H, H4,6). 13C NMR (C6D5Cl): δ -1.4 (q, J CH
)
1
1
8F, m-C6F5). 31P NMR (C6D5Cl): δ -46.3 (br s).
139, InMe), 0.4 (q, J CH ) 138, MeCN), 24.2 (q, J CH ) 127,
[(iP r 2-ATI)In (Me)(NMe2P h )][MeB(C6F5)3] (14) an d [(iP r 2-
ATI)In (Me)(P Me3)][MeB(C6F 5)3] (15). NMR data for 14 and
15 are identical to data for 10 and 13, respectively, except for
the anion resonances.
1
1
CHMe2), 48.5 (d, J CH ) 137, CHMe2), 116.8 (d, J CH ) 152,
C5), 118.8 (br s, MeCN), 123.8 (d, J CH ) 162, C3,7), 136.9 (d,
1
1
1
1J CF ) 243, C6F5), 137.0 (d, J CH ) 155, C4,6), 138.7 (d, J CF
)
245, C6F5), 148.9 (d, 1J CF ) 241, C6F5), 158.3 (s, C1,2); the ipso-
C6F5 resonance was not observed. 11B NMR (C6D5Cl): δ -16.5
(s). 19F NMR (C6D5Cl): δ -132.1 (m, 8F, o-C6F5), -162.4 (t,
3J FF ) 20, 4F, p-C6F5), -166.5 (m, 8F, m-C6F5).
X-r a y Str u ctu r a l Deter m in a tion s. Crystal data, data
collection details, and solution and refinement procedures are
collected in Table 7, and full details are provided in the
Supporting Information. The ORTEP diagrams were drawn
with 30% probability ellipsoids. All non-hydrogen atoms were
refined with anisotropic displacement coefficients unless oth-
erwise indicated. All hydrogen atoms were included in the
structure factor calculation at idealized positions and were
allowed to ride on the neighboring atoms with relative aniso-
tropic displacement coefficients. Additional comments specific
to each structure follow.
[(iP r 2-ATI)In (Me)(Me2CO)][B(C6F 5)4] (12). 1H NMR
(C6D5Cl): δ 0.73 (s, 3H, InMe), 1.18 (d, J HH ) 5.8, 12H,
3
3
CHMe2), 1.87 (br s, 6H, Me2CO), 3.87 (sept, J HH ) 5.8, 2H,
CHMe2), 6.71 (t, 3J HH ) 9.4, 1H, H5), 6.81 (d, 3J HH ) 11.3, 2H,
1
H3,7), 6.87 (m, 2H, H4,6). 13C NMR (C6D5Cl): δ -1.0 (q, J CH
)
1
1
135, InMe), 24.3 (q, J CH ) 127, CHMe2), 31.0 (q, J CH ) 128,
1
1
Me2CO), 48.4 (d, J CH ) 137, CHMe2), 117.0 (d, J CH ) 152,
C5), 124.4 (d, J CH ) 161, C3,7), 136.8 (d, J CF ) 243, C6F5),
1
1
137.1 (d, J CH ) 156, C4,6), 138.7 (d, J CF ) 245, C6F5), 148.9
(iP r 2-ATI)In Cl2 (3) a n d (iP r 2-ATI)In Me2 (4). Crystals
were grown from a saturated pentane solution to -78 °C.
1
1
(d, J CF ) 241, C6F5), 158.7 (s, C1,2), 221.1 (s, CdO); the ipso-
1

1176 Organometallics, Vol. 21, No. 6, 2002
Delpech et al.
[{1,2-(N i P r )2-5-C P h 3-c y c lo h e p t a -3,6-d ie n e }I n Me 2]-
[B(C6F 5)4] (5). Crystals were grown by slow evaporation of
chlorobenzene solution of at 23 °C.
[(iP r 2-ATI)In (Me)(NMe2P h )][B(C6F 5)4] (10). The complex
was dissolved in chlorobenzene and pentane was slowly
layered on top (chlorobenzene/pentane ) 1:2), resulting in slow
crystal growth. The isopropyl group on N(2) is equally disor-
dered over two positions and was refined with an idealized
geometry.
[(iP r 2-ATI)In Me][B(C6F 5)4]‚C6H5Cl (6‚C6H5Cl). The com-
plex was dissolved in chlorobenzene, and pentane was slowly
layered on top (chlorobenzene/pentane ) 1:2) resulting in slow
crystal growth. All non-hydrogen atoms except C(104) and
C(105) were refined with anisotropic displacement coefficients.
There are two symmetry-independent molecules in the asym-
metric unit; one molecule is equally disordered over two
positions and was refined with an idealized geometry. There
are also two C6H5Cl molecules equally disordered over two
positions.
Ack n ow led gm en t. This work was supported by
DOE grant DE-FG02-88ER13935.
Su p p or tin g In for m a tion Ava ila ble: NMR data for an-
ions and Lewis bases in C6D5Cl and details of X-ray crystal-
lographic analyses of 3, 4, 5, 6‚PhCl, and 10. This material is
available free of charge via the Internet at http://pubs.acs.org.
(iP r 2-ATI)In (C6F 5)2 (9). Crystals were grown from pentane
at 23 °C.
OM010578X