Preparation and characterization of nickel complexes with η-indenyl ligands bearing a pendant aminoalkyl chain

Article abstract of DOI:10.1021/om9907122

The aminoindenyl complexes {Ind(CH₂)_3,4N(t-Bu)H}Ni(PPh₃)Cl (7, 8) and {Ind(CH₂)_2,3NMe₂}Ni(PPh₃)Cl (9, 10) have been prepared and characterized by spectroscopy and, in the case of 7 and 9, by X-ray structural studies. Although there is no interaction between the Ni center and the amine moiety of these complexes in the solid state, solution spectra point to a temperature-dependent, intramolecular N→Ni coordination in complex 9 and a more facile, intermolecular interaction in 10. Abstraction of Cl^- from these complexes led to the formation of the cations [{η³:η⁰-Ind(CH₂)_3,4N(t-Bu)H}Ni (PPh₃)₂]⁺ and [{η³:η¹-Ind(CH₂) _2,3NMe₂}Ni(PPh₃)]⁺ (11, 12). The origin of the observed differences in the reactivities of these complexes is discussed in terms of the lengths of the tether and the nature of the N-substituents.

Full text of DOI:10.1021/om9907122

Organometallics 2000, 19, 1507-1513
1507
P r ep a r a tion a n d Ch a r a cter iza tion of Nick el Com p lexes
w ith η-In d en yl Liga n d s Bea r in g a P en d a n t Am in oa lk yl
Ch a in
Laurent F. Groux, Francine Be´langer-Garie´py, Davit Zargarian,* and
Rainer Vollmerhaus†
De´partement de chimie, Universite´ de Montre´al, Montre´al, Que´bec, Canada H3C 3J 7
Received September 9, 1999
The aminoindenyl complexes {Ind(CH2)3,4N(t-Bu)H}Ni(PPh3)Cl (7, 8) and {Ind(CH2)2,3
-
NMe2}Ni(PPh3)Cl (9, 10) have been prepared and characterized by spectroscopy and, in the
case of 7 and 9, by X-ray structural studies. Although there is no interaction between the
Ni center and the amine moiety of these complexes in the solid state, solution spectra point
to a temperature-dependent, intramolecular NfNi coordination in complex 9 and a more
facile, intermolecular interaction in 10. Abstraction of Cl- from these complexes led to the
formation of the cations [{η3:η0-Ind(CH2)3,4N(t-Bu)H}Ni(PPh3)2]+ and [{η3:η1-Ind(CH2)2,3
-
NMe2}Ni(PPh3)]+ (11, 12). The origin of the observed differences in the reactivities of these
complexes is discussed in terms of the lengths of the tether and the nature of the
N-substituents.
Ch a r t 1
In tr od u ction
There has been a growing interest over the recent
years in the reactivities of complexes containing Cp-type
ligands bearing amine- or amide-functionalized side
chains, Cp∧NRn (∧ ) tethering side chains). A few of
these compounds are excellent catalysts for the polym-
erization of olefins,1 while others catalyze the dehydro-
polymerization of silanes2 and show other intriguing
properties.3 A survey of the literature reveals that most
of the reported studies on Cp∧NRn systems have focused
on the complexes of early transition metals (groups 3-6)
and relatively few complexes of this type are known for
later metals. This is especially true in the case of group
10 metals, for which only a few examples have been
reported by Fischer (e.g., (η5:η0-Cp∧NMe2)Ni(CO)-
(SnMe3), (η5:η0-Cp∧NMe2)Ni(PPh3)(Si(SiMe3)3), and
(η5:η1-Cp∧NMe2)NiI)4 and J utzi (e.g., (η5:η0-Cp∧NMe2)-
Ni(PMe3)I, (η5:η0-Cp∧NMe2)Pd(η3-allyl), and (η5:η0-
Cp∧NH2)PtMe3).5
compounds bearing amino- and amidoalkyl side chains
tethered to the Ind ligand. Thus, we set out to prepare
the first examples of neutral and cationic Ind∧NR2
complexes of nickel with both dangling (η0) and coordi-
nating (η1) N-functionalities, as illustrated in Chart 1.
The present paper reports the preparation of the
Our interest in the structural properties and catalytic
activities of the nickel indenyl complexes IndNi(PR3)X6
prompted us to explore the chemistry of analogous
complexes (η3:η0-Ind∧NRR′)Ni(PPh3)X (∧ ) (CH2)2-4
;
R,R′ ) H, Me, t-Bu; X ) Cl, Me, Bu) and [(η3:η1-
† Present address: Technische Universiteit Eindhoven, Postbus 513,
5600 MB Eindhoven, The Netherlands.
Ind(CH2)2NMe2)Ni(PPh3)]+.
(1) (a) Shapiro, P. J .; Bunel, E.; Schaefer, W. P.; Bercaw, J . E.
Organometallics 1990, 9, 867. (b) Piers, W. E.; Shapiro, P. J .; Bunel,
E.; Bercaw, J . E. Synlett 1990, 1, 74. (c) Shapiro, P. J .; Cotter, W. D.;
Schaefer, W. P.; Labinger, J . A.; Bercaw, J . E. J . Am. Chem. Soc. 1994,
116, 4623. (d) Emrich, R.; Heinemann, O.; J olly, P. W.; Kru¨ger, C.;
Verhovnik, G. P. J . Organometallics 1997, 16, 1511. (e) Blais, M. S.;
Chien, J . C. W.; Rausch, M. D. Organometallics 1998, 17, 3775.
(2) Choi, N.; Onozawa, S.; Sakakura, T.; Tanaka, M. Organometallics
1997, 16, 2765.
(3) J utzi, P.; Redeker, T. Eur. J . Inorg. Chem. 1998, 663.
(4) (a) Fischer, R. A.; Nlate, S.; Hoffmann, H.; Herdtweck, E.;
Blu¨mel, J . Organometallics 1996, 15, 5746. (b) Nlate, S.; Herdtweck,
E.; Fischer, R. A. Angew. Chem., Int. Ed. Engl. 1996, 35, 1861. (c)
Weiss, J .; Herdtweck, E.; Nlate, S.; Mattner, M.; Fischer, R. A. Chem.
Ber. 1996, 129, 297.
Resu lts a n d Discu ssion
P r ep a r a tion of th e Liga n d s. The syntheses of the
aminoindenyl ligands 1-6 are outlined in Scheme 1.
(6) (a) Huber, T. A.; Be´langer-Garie´py, F.; Zargarian, D. Organo-
metallics 1995, 14, 4997. (b) Bayrakdarian, M.; Davis, M. J .; Reber,
C.; Zargarian, D. Can. J . Chem. 1996, 74, 2115. (c) Huber, T. A.;
Bayrakdarian, M.; Dion, S.; Dubuc, I.; Be´langer-Garie´py, F.; Zargarian,
D. Organometallics 1997, 16, 5811. (d) Vollmerhaus, R.; Be´langer-
Garie´py, F.; Zargarian, D. Organometallics 1997, 16, 4762. (e) Fon-
taine, F.-G.; Kadkhodazadeh, T.; Zargarian, D. J . Chem. Soc., Chem.
Commun. 1998, 1253. (f) Dubuc, I.; Dubois, M.-A.; Be´langer-Garie´py,
F.; Zargarian, D. Organometallics 1999, 18, 30.
(5) J utzi, P.; Redeker, T.; Stammler, H.-G.; Neumann, B. J . Orga-
nomet. Chem. 1995, 498, 127.
10.1021/om9907122 CCC: $19.00 © 2000 American Chemical Society
Publication on Web 03/23/2000

1508 Organometallics, Vol. 19, No. 8, 2000
Groux et al.
Sch em e 1
F igu r e 1. ORTEP plot of complex 7 with atom-numbering
scheme. Selected bond lengths (Å) and angles (deg): Ni-P
) 2.181(3), Ni-Cl ) 2.187(2), Ni-C1 ) 2.135(6), Ni-C2
) 2.057(6), Ni-C3 ) 2.028(6), Ni-C3a ) 2.296(7), Ni-C7a
) 2.357(8), C1-C2 ) 1.409(10), C2-C3 ) 1.423(9), C3-
C3a ) 1.456(10), C3a-C7a ) 1.422(9), C7a-C1 ) 1.452-
(9), C1-C8 ) 1.497(9); Cl-Ni-P ) 96.75(12), Cl-Ni-C3
) 162.4(2), Cl-Ni-C2 ) 122.7(2), Cl-Ni-C1 ) 95.8(2),
P-Ni-C1 ) 166.0(2), P-Ni-C2 ) 130.6(2), P-Ni-C3 )
99.2(2), C1-Ni-C2 ) 39.2(3), C1-Ni-C3 ) 67.0(3), C2-
Ni-C3 ) 40.8(3).
The reaction of IndLi with an excess of 1,3-dibromopro-
pane in Et2O produced the desired (3-bromopropyl)-
indene in addition to the undesired byproduct 1,3-
diindenylpropane. The former was isolated in ca. 60%
yield after vacuum distillation and subsequently reacted
with t-BuNH2 to give the HBr salt of Ind(CH2)3N(t-Bu)H
(1) as an air-stable, white powder in ca. 85% yield. Using
1,4-dibromopropane in this synthesis yields the desired
aminoindenyl ligand with a butyl side chain (2), whereas
1,2-dibromopropane leads to a known7 spirocyclic byprod-
uct. Using BzNH2 (Bz ) PhCH2) instead of t-BuNH2
gave Ind(CH2)3N(Bz)H (3). The NMe2 and NH2 ligands
(4-6) were prepared by reacting IndLi with X(CH2)n-
NR′2 (n ) 2, 3; X ) Cl, Br; R′ ) Me, H; Scheme 1).
Typ e I Com p lexes. The preparation of (η3:η0-amino-
indenyl)nickel complexes was attempted by reacting
(PPh3)2NiCl2 with the singly deprotonated aminoin-
denes. Thus, reacting [Ind(CH2)3N(t-Bu)H]- with (PPh3)2-
NiCl2 in Et2O gave a dark red solution from which the
complex 7 could be isolated in 63% yield; similar
protocols with the ligands 2, 4, and 5 allowed the
formation of the Ni complexes 8-10, respectively
(Scheme 1). These compounds have been characterized
by spectroscopy and, in the case of 7 and 9, by X-ray
diffraction studies (vide infra).
31P{1H} spectra contained only the signal attributed to
uncoordinated PPh3.
It is conceivable that the complexes (η3:η0-Ind(CH2)3-
NRH)Ni(PPh3)Cl (R ) Bz, H) form at first but decom-
pose afterward as a result of the interaction of the amine
moieties with the Ni center (either intra- or intermo-
lecularly). To test the validity of this supposition, we
reacted the otherwise stable complex (1-Me-Ind)Ni-
(PPh3)Cl with a number of amines and found that it
decomposed readily upon contact with BzNH2 and
pyridine; BzN(Me)H also caused the decomposition of
this complex, but at a slower rate, while t-BuNH2 and
Et3N did not react at all. We conclude, therefore, that
the stabilities of complexes (Ind∧NRR′)Ni(PPh3)Cl de-
pend on the nature of the substituents on the amine
moiety: the NH(t-Bu) and NMe2 groups give the rela-
tively stable species 7-10, whereas NHBz and NH2
groups allow side reactions which eventually lead to the
decomposition of the complexes.
In contrast to the syntheses of 7-10, the preparation
of the analogous derivatives with the aminoindenyl
ligands Ind(CH2)3NHR (R ) Bz (3), H (6)) did not result
in the isolation of stable compounds. For instance,
addition of an Et2O solution of singly deprotonated 3
(i.e., [Ind(CH2)3N(PhCH2)H]-) to the dark green Et2O
suspension of (PPh3)2NiCl2 resulted, at first, in the
appearance of the red color characteristic of the com-
pounds (Ind)Ni(PR3)X; however, the reaction mixture
turned brown and then beige over a few minutes and
no tractable compound could be isolated in the end.
Lowering the temperature of the reaction did not
prevent the decomposition of this material. A similar
observation was made in the reaction of ligand 6. The
1H NMR spectra of the reaction mixtures in both
reactions showed broad, featureless signals character-
istic of paramagnetic or polymeric species, while the
Ch a r a ct er iza t ion a n d Dyn a m ic Beh a vior of
(In d ∧NRR′)Ni(P P h 3)Cl. The general features of the
NMR spectra obtained for compounds 7 and 8 are
similar to those of the analogous complexes (1-Me-Ind)-
1
Ni(PPh3)Cl. For instance, the H NMR resonances for
the H2 and H3 protons appear at ca. 6.5 and 3.5 ppm,
respectively, while the 31P{1H} NMR spectra consist of
a singlet resonance at ca. 33 ppm; these are very close
to the corresponding resonances for (1-Me-Ind)Ni(PPh3)-
Cl,6c indicating that the geometry around the Ni atom
and the hapticity of the Ind ligand in 7 and 8 are very
similar to those found in (1-Me-Ind)Ni(PPh3)Cl. The
solid-state structure of 7 (Figure 1, vide infra) and
variable-temperature 1H and 13C{1H} NMR experiments
showed that the N(t-Bu)H moiety in these complexes is
not coordinated to Ni. Similarly, the X-ray structure of
complex 9 (Figure 2; vide infra) showed that the NMe2
moiety in this compound is not coordinated to the Ni
(7) Lemieux, R. P.; Beak, P. J . Org. Chem. 1990, 55, 5454.

Nickel Complexes with η-Indenyl Ligands
Organometallics, Vol. 19, No. 8, 2000 1509
in question is a neutral compound in which the Cl ligand
remains coordinated to Ni. It is not certain, however,
whether the Ind moiety remains η3-coordinated (giving
an 18-electron species) or slips into an η1-mode (giving
a 16-electron species).
In contrast to the above-described dynamic behavior
displayed by complex 9, complex 10 was found to
undergo a gradual and irreversible transformation in
solution, one which ultimately prevented the purifica-
tion and complete characterization of this compound.
Thus, repeated recrystallizations of complex 10 precipi-
tate solid samples which are increasingly insoluble and
give poorly resolved NMR spectra. For example, whereas
9 and freshly prepared samples of 10 were soluble in
Et2O, C6H6, toluene, etc., the solids obtained after
recrystallizing 10 were soluble only in DMSO. Moreover,
1
whereas the H and 13{1H} NMR spectra of pre-recrys-
tallization samples of 10 contained well-resolved signals
quite similar to those of complex 9, the aged solutions
and recrystallized samples of 10 showed broad, feature-
less peaks. We believe that this “decomposition” of
complex 10 is caused by the interaction between the
NMe2 moiety and the Ni center and suggest that the
longer side chain in this compound allows an intermo-
lecular coordination which results in the formation of a
sparingly soluble polymeric species.
F igu r e 2. ORTEP plot of complex 9 with atom-numbering
scheme. Selected bond lengths (Å) and angles (deg): Ni-P
) 2.1838(15), Ni-Cl ) 2.1763(14), Ni-C1 ) 2.137(4), Ni-
C2 ) 2.060(4), Ni-C3 ) 2.028(5), Ni-C3a ) 2.283(5), Ni-
C7a ) 2.341(4), C1-C2 ) 1.405(6), C2-C3 ) 1.440(6), C3-
C3a ) 1.419(6), C3a-C7a ) 1.424(6), C7a-C1 ) 1.464(6),
C1-C8 ) 1.487(5); Cl-Ni-P ) 98.01(6), Cl-Ni-C3 )
162.44(13), Cl-Ni-C2 ) 122.61(15), Cl-Ni-C1 ) 96.09-
(13), P-Ni-C1 ) 165.87(13), P-Ni-C2 ) 130.41(14),
P-Ni-C3 ) 99.32(13), C1-Ni-C2 ) 39.07(15), C1-Ni-
C3 ) 66.65(17), C2-Ni-C3 ) 41.25(18).
Solid -Sta te Str u ctu r es of 7 a n d 9. As seen in
Figures 1 and 2, the nickel centers in both 7 and 9 are
within reasonable bonding distance from the P (ca. 2.18
Å), Cl (ca. 2.19 Å), C1 (ca. 2.14 Å), C2 (ca. 2.06 Å), and
C3 (ca. 2.03 Å) atoms but considerably farther away
from C3a (average 2.29 Å) and C7a (average 2.35 Å).
The geometry around the Ni is irregular but may be
described as distorted square planar with C1dC2 oc-
cupying a single coordination site. The planes formed
by P, Ni, and Cl on one hand and C1, C2, and C3 on
the other are nearly perpendicular to each other. In both
structures, the aminoalkyl side chain is oriented away
from the Ni center.
Sch em e 2
The main features of 7 and 9 are very similar to those
present in the solid-state structure of (1-Me-Ind)Ni-
(PPh3)Cl.6c For instance, all three structures exhibit
virtually identical (i.e., within (3σ) Ni-P (2.181(3),
2.1838(15), and 2.1782(11) Å) and Ni-Cl (2.187(2),
2.1763(14), and 2.1865(10) Å) bond lengths. Moreover,
in all three structures the distortion of the Ind hapticity
away from an η5 mode and toward a fairly nonsymmet-
ric η3 coordination is reflected in the unequal Ni-C and
C-C bond lengths: Ni-C7a > Ni-C3a . Ni-C1 > Ni-
C2 > Ni-C3 and C1-C7a (1.452(9) Å) ≈ C3-C3a
(1.456(10) Å) > C3-C2 (1.423(9) Å) > C2-C1 (1.409-
(10) Å). These distortions are attributed to the tendency
of the d8 Ni center to form 16-electron complexes (η5 f
η3 slippage of Ind) and the unequal trans influences of
the PPh3 and Cl groups (unsymmetrical coordination
of Ind).6c
atom in the solid state; in this case, however, the
solution spectra indicated the presence of relatively fast
equilibria which convert 9 and 10 into species involving
NfNi interactions, as described below.
The first indication of a dynamic process involving
1
complex 9 was the observation that some of the H and
13C{1H} NMR signals were either broadened or missing
from the ambient and higher temperature spectra (up
to +50 °C) of this complex; at lower temperatures, the
broad peaks sharpened and the missing peaks emerged.
Significantly, the peaks corresponding to the nuclei on
the side chain were the most affected during this
process. In addition, the variable-temperature 31P{1H}
NMR spectra showed that the singlet resonance for 9
moved from ca. 31 ppm at 22 °C to ca. 38 ppm at +50
°C; cooling the sample to room temperature resulted in
the reappearance of the signals for 9. These observations
imply that in solution the η3:η0-aminoindenyl complex
9 is in equilibrium with a species in which the NMe2
moiety reversibly coordinates to the Ni center (Scheme
2). Given that the spectral features of this new complex
are very different from those of the cationic complex
which would arise from the displacement of Cl by the
amine moiety (vide infra), we believe that the species
Typ e II Com p lexes. We reacted the complexes 7-10
with AgBF4, NaBPh4, or AlCl3 in order to abstract the
Cl- ligand from these complexes and facilitate the
formation of the target η3:η1 cationic species. Abstraction
of Cl- from 7 resulted in the formation of a major species
displaying an AB set of resonances in the 31P{1H} NMR
spectrum of the reaction mixture (ca. 34 and 32 ppm,
dd, 2J P-P ) 26 Hz); the spectrum also contained a singlet

1510 Organometallics, Vol. 19, No. 8, 2000
Groux et al.
Sch em e 3
resonance at ca. 24 ppm corresponding to a minor
product. The major product was readily identified as
[{η3:η0-Ind(CH2)3NH(t-Bu)}Ni(PPh3)2]+ on the basis of
comparison to the 31P{1H} NMR spectrum of the fully
characterized6d compound [(1-Me-Ind)Ni(PPh3)2]+, which
displays a similar AB signal. The inequivalence of the
PPh3 ligands in these compounds is consistent with the
hindered rotation of the unsymmetrically substituted
Ind ligands. When the Cl- abstraction from 7 is carried
out in the presence of an excess of PPh3, only the bis-
(phosphine) cation is obtained, suggesting that the
minor product observed in the original reaction might
be the desired [{η3:η1-Ind(CH2)3NH(t-Bu)}Ni(PPh3)]+.
Abstraction of the Cl- ligand from complex 8 with or
without added PPh3 gave only the bis-PPh3 cation [{η3:
η0-Ind(CH2)4NH(t-Bu)}Ni(PPh3)2]+. These results indi-
cate that NfNi coordination is fairly unfavorable in the
η3:η0-aminoindenyl complexes bearing the N(t-Bu)H
moiety. Consequently, the electronically and coordina-
tively unsaturated species [{η3:η0-Ind(CH2)nNH(t-Bu)}-
Ni(PPh3)]+ resulting from the abstraction of Cl- from 7
and 8 undergo a phosphine redistribution reaction to
form the observed bis-PPh3 cations (Scheme 3).
Typ e III a n d IV Com p lexes. All our attempts to
prepare phosphine-free η3:η1 complexes of the type III
have resulted in the decomposition of these materials.
It appears that strong trans-influence ligands such as
phosphines are needed to stabilize the coordination of
the Ind moiety. We have also explored the deprotonation
of the N(t-Bu)H moiety in complexes 7 and 8 as a route
to neutral {η3:η1-Ind∧N(t-Bu)}Ni(PPh3) complexes of the
type IV. Reacting these complexes with LiN(i-Pr)2 led
to side reactions which produced a complex mixture of
intractable products. Attempts at deprotonation with
BuLi at both low and high temperatures led instead to
the formation of the Ni-Bu complex; analogous reac-
tions with MeLi gave the Ni-Me analogue (Scheme 3).
The identities of these compounds were established by
1
comparing their H and 31P{1H} NMR spectra to those
of the analogous methyl complex (1-Me-Ind)(PPh3)Ni-
Me.6c For example, the downfield shifts in the 31P{1H}
NMR resonances of these compounds (ca. 33 ppm in the
Ni-Cl compound vs 46-48 ppm in the Ni-Me and Ni-
Bu analogues) are characteristic for Ni-C bond forma-
tion in these compounds. Additional evidence for this
assignment includes the characteristically upfield 1H
NMR resonances for the Ni-CHn protons (ca. -0.7 ppm
for Ni-Me) and the downfield shift of the H3 signal (ca.
3.4 ppm for 7 and ca. 4.2 ppm for its Ni-Me derivative);
the latter results from the change in the hapticity of
the Ind ring brought about by the stronger trans
influences of alkyl ligands compared to Cl.
The formation of these Ni-alkyl complexes raised the
possibility that the target amidoindenyl complexes
might be accessible via the intramolecular deprotona-
tion of the dangling N-H bonds with the Ni-R moiety;
this type of alkane elimination reaction has precedents
in early-metal complexes8 but did not take place with
our Ni-Me and Ni-Bu compounds even upon extended
heating (Scheme 3). We also attempted the preparation
of type IV complexes via direct metathetic reactions
between (PPh3)2NiCl2 and the dianionic ligands [1]2-
and [3]2-. These reactions gave deep green-blue solu-
tions whose 1H NMR spectra consisted of broad, fea-
In contrast to the case for complexes 7 and 8, Cl-
abstraction from 9 gave a new species which showed a
singlet resonance at ca. 29 ppm in its 31P{1H} NMR
spectrum instead of the AB pattern characteristic of the
above-discussed bis-PPh3 cations. Though we have not
succeeded in our attempts to obtain suitable single
crystals of this new compound for X-ray diffraction
studies, the spectral and analytical data collected
strongly support its formulation as [{η3:η1-Ind(CH2)2-
NMe2}Ni(PPh3)]+ (11) (Scheme 3). Monitoring the reac-
tion of complex 11 with a ca. 30-fold excess of PPh3 by
31P{1H} NMR (CDCl3) showed the gradual emergence
of the characteristic signals for the bis(phosphine) cation
(two doublets at 36.4 and 32.5 ppm, 2J P-P ) 20 Hz); the
conversion was complete within 60 min. In the case of
complex 10, Cl- abstraction also leads to a new complex
which shows a singlet at 26 ppm in its 31P{1H} NMR
spectrum (Scheme 3). We conclude, therefore, that the
ease of formation of η3:η1 cationic complexes of the type
II is strongly influenced by the coordinating ability of
the amine moiety, with the NMe2 moiety being more
suitable for this purpose than N(t-Bu)H.
(8) Mu, Y.; Piers, W. E.; MacQuarrie, D. C.; Zaworotko, M. J .; Young,
V. G. Organometallics 1996, 15, 2720.
(9) Groux, L. F.; Be´langer-Garie´py, F.; Zargarian, D. Acta Crystal-
logr., Sect. C, in press.

Nickel Complexes with η-Indenyl Ligands
Organometallics, Vol. 19, No. 8, 2000 1511
tureless resonances while the 31P{1H} NMR spectra
showed no signals; no tractable solids could be isolated
from the reaction mixtures. These observations are
reminiscent of the results from our previous studies on
the preparation of the (nonchelating) amido compounds
IndNi(PPh3)(NRR′); these studies revealed that the Ni-
NR2 moiety in these compounds is very labile, preclud-
ing the isolation of thermally stable complexes except
when the R substituents are strongly electron with-
drawing.6f
Con clu sion . New complexes of the type {η3:η0-
Ind∧NRR′}Ni(PPh3)Cl (7-10) can be synthesized with
NMe2 and N(t-Bu)H moieties, but the NH2 and N(Bz)H
analogues decompose during synthesis. The N(t-Bu)H
and NMe2 moieties in these compounds are oriented
away from the Ni atom in the solid state. The interac-
tion of the N(t-Bu)H functionality with the Ni center in
complexes 7 and 8 is also weak in the solution, whereas
the coordination of the NMe2 moiety to Ni in the
solutions of complexes 9 and 10 can be detected. The
NfNi interaction appears to be intramolecular and
reversible in the case of 9 but irreversible and inter-
molecular in the case of 10. Therefore, the stability of
these η3:η0-aminoindenyl compounds is modulated by
the nature of the N-substituents as well as the length
of the tethering chain. The cationic species [{η3:η0-
Ind∧N(t-Bu)H}Ni(PPh3)2]+, [{η3:η1-Ind∧NMe2}Ni(PPh3)]+,
and [{η3:η0-Ind∧NMe2}Ni(PPh3)2]+ were prepared by
abstracting the Cl- ligand from the neutral precursors.
Experiments aimed at evaluating the catalytic reactivi-
ties of the η3:η0- and η3:η1-aminoindenyl compounds are
in progress.
144.7 & 144.2 & 141.9 (C3a, C7a, C3), 128.5 & 126.0 & 124.6
& 123.6 (C4-7), 118.8 (C2), 57.7 (CMe3), 41.7 (CH2N), 37.6
(C1), 25.9 (IndCH2), 24.8 (CH2CH2CH2), 24.4 (Me). HRMS of
acid-free ligand: 230.191 70 (calcd 230.190 87). Anal. Calcd
for C16H23N‚HBr: C, 61.94; H, 7.80; N, 4.51. Found: C, 61.67;
H, 7.81; N, 4.51.
In d H(CH2)4N(t-Bu )H‚HBr (2‚HBr ). The above procedure
for the preparation of IndH(CH2)3NH(t-Bu) was repeated with
1
IndH(CH2)4Br to give a white powder (1.47 g, 28%). H NMR
of the HBr salt (CDCl3): δ 8.88 (br, NH2), 7.43 and 7.30 (d,
3
3J H-H ) 7.3, H4 & H7), 7.24 and 7.17 (ps t, J H-H ) 7.4, H5 &
3
H6), 6.21 (s, H2), 3.32 (d, J H-H ) 1.7, H1), 2.96 (br, CH2N),
3
3
2.57 (t, J H-H ) 7.3, IndCH2), 2.25 (quint, J H-H ) 8.1,
3
NCH2CH2), 1.77 (quint, J H-H ) 7.8, IndCH2CH2), 1.50 (s,
t-Bu). 13C{1H} NMR of the HBr salt (CDCl3): δ 145.0 & 144.3
& 143.2 (C3a, C7a, C3), 128.2 & 125.9 & 124.4 & 123.6 (C4-
7), 118.7 (C2), 57.6 (NCMe3), 41.9 (CH2N), 37.6 (C1), 27.1
(IndCH2), 26.4 & 25.9 (CH2CH2CH2N), 25.5 (Me). Anal. Calcd
for C17H25N‚HBr: C, 62.96; H, 8.08; N, 4.32. Found: C, 62.57;
H, 8.13; N, 4.29.
In d H(CH2)3N(CH2P h )H‚HCl (3‚HCl). IndH(CH2)3Cl (932
mg, 4.84 mmol) and NaI (725 mg, 4.84 mmol) were stirred in
CH3CN (20 mL) for 10 min at room temperature, followed by
the addition of PhCH2NH2 (2.5 g, 24 mmol) and heating to
reflux for 16 h. The reaction mixture containing a white
precipitate was evaporated to dryness and extracted with Et2O
(ca. 50 mL) and a 10% solution of HCl (ca. 75 mL). The solid
suspended between the two phases was isolated by filtration
and recrystallized from MeOH/Et2O (2:1) to yield 890 mg of a
white solid. Two further recrystallizations were necessary to
produce analytically pure product (766 mg, 52%). The acid-
free product was obtained by deprotonation with NaOH or
1
BuLi. H NMR of acid-free ligand (C6D6): δ 7.3-7.0 (m), 5.92
3
(br t, H2), 3.55 (s, CH2Ph), 3.02 (br d, J H-H ) 2, H1), 2.45 (t,
3
3J H-H ) 7.2, CH2CH2CH2), 1.68 (quint, J H-H ) 7.2, CH2CH2-
CH2), 0.68 (br, NH). 13C{1H} NMR of HCl salt (CDCl3): δ 143.8
& 142.3 (C3a, C7a), 128.6 & 128.1 (o- & m-C), 127.8, 127.5,
125.4, 123.9, 123.1, 118.3 (C2), 51.6 (PhCH2N), 46.7 (NCH2-
CH2), 37.0 (C1), 25.5 (IndCH2), 24.4 (CH2CH2CH2). Anal. Calcd
for C19H21N‚HCl: C, 76.11; H, 7.40; N, 4.67. Found: C, 76.03;
H, 7.50; N, 4.69. The solid-state structure of the HBr salt of
this ligand has been reported.9
Exp er im en ta l Section
Gen er a l Com m en ts. All manipulations and experiments
were performed under an inert atmosphere of nitrogen using
standard Schlenk techniques and/or in an argon-filled glove-
box. Dry, oxygen-free solvents were employed throughout. The
elemental analyses were performed by Laboratoire d’analyse
e´le´mentaire (Universite´ de Montre´al). An AMXR400 spectrom-
In d H(CH2)3NMe2 (5). A mixture of BuLi (6.9 mL of a 2.5
M solution) and IndH (1.74 g, 15 mmol) in Et2O was stirred
for 3 h and added dropwise to an Et2O mixture (ca. 100 mL)
of Cl(CH2)3NMe2‚HCl (1.90 g, 12 mmol) and BuLi (6.0 mL of
a 2.5 M solution). The resultant mixture was stirred for 4 days
at room temperature and extracted with a 10% HBr solution.
The aqueous portion was neutralized (KOH) and extracted
with hexane; the hexane portion was dried (MgSO4) and
1
eter was used for recording the ambient-temperature H (400
MHz), 13C{1H} (100.56 and 75.44 MHz), and 31P{1H} (161.92
MHz) NMR spectra; the variable-temperature NMR studies
were carried out on a Varian VXR4000 spectrometer. The
ligand IndCH2CH2NMe2 (4) has been reported previously.1e
The remaining (aminoalkyl)indenes were prepared either by
the reaction of IndLi with the appropriate alkyl halides
X(CH2)nNR2 (n ) 2, 3; X ) Cl, Br; R ) Me, H), which were
purchased from Aldrich and used as received, or by reacting
the appropriate amine with Ind(CH2)nX (n ) 3, 4; X ) Br, I),
as described below.
1
evaporated to give 1.15 g of a pale yellow oil (47% yield). H
3
NMR (C6D6): δ 7.38 and 7.29 (d, J H-H ) 9, H4 & H7), 7.21
3
and 7.11 (t, J H-H ) 8, H5 & H6), 6.02 (s, H2), 3.07 (s, H1),
2.55 (t, 3J H-H ) 8, CH2N), 2.22 (t, 3J H-H ) 8, IndCH2), 2.14 (s,
3
1
NMe2), 2.10 (quint, J H-H ) 8, CH2CH2N). H NMR (CDCl3):
δ 7.48 and 7.37 (d, 3J H-H ) 8, H4 & H7), 7.29 and 7.20 (t, 3J H-H
In d H(CH2)3N(t-Bu )H‚HBr (1‚HBr ). IndH(CH2)3Br (7.04
g, 29.7 mmol) and t-BuNH2 (ca. 15 mL) were stirred in CH3-
CN (ca. 30 mL) at room temperature and then refluxed for 24
h, during which time a white precipitate appeared. The final
reaction mixture was evaporated to dryness, and the resulting
white solid was recrystallized from MeOH/Et2O (2:1), yielding
a white powder (8.10 g, 87%). The acid-free ligand was
obtained by deprotonation with KOH or BuLi. 1H NMR of the
3
) 8, H5 & H6), 6.22 (s, H2), 3.33 (s, H1), 2.58 (t, J H-H ) 8,
CH2N), 2.40 (t, 3J H-H ) 8, IndCH2), 2.27 (s, NMe2), 1.88 (quint,
3J H-H ) 8, CH2CH2N). 13C{1H} NMR (CDCl3): δ 145.3 & 144.4
& 144.0 (C3a, C7a, C3), 127.7 & 125.6 & 124.4 & 123.6 (C4-
7), 118.8 (C2), 59.7 (CH2N), 45.4 (NMe), 37.6 (C1), 25.9 & 25.4
(IndCH2CH2). Anal. Calcd for C14H19N: C, 83.53; H, 9.51; N,
6.96. Found: C, 83.58; H, 9.63; N, 6.85.
3
acid-free ligand (CD3CN): δ 7.44 and 7.38 (d, J H-H ) ca. 7.3,
In d H(CH2)3NH2‚HBr (6‚HBr ). Using the above procedure
for the preparation of IndH(CH2)3NMe2 (5) with Br(CH2)3NH2‚
HBr gave a white solid which remained suspended between
the organic and aqueous layers during the extraction step.
Filtration gave the desired IndH(CH2)3NH2‚HBr (2.48 g, 88%).
1H NMR of the acid-free ligand (CDCl3): δ 7.45 and 7.36 (d,
3
H4 & H7), 7.27 and 7.18 (t, J H-H ) 7.2, H5 & H6), 6.24 (br s,
3
H2), 3.31 (br s, H1), 2.60 (m, CH2CH2CH2), 1.72 (quint, J H-H
) 7.4, CH2CH2CH2), 1.03 (s, C(CH3)3). 1H NMR of the HBr
salt (CDCl3): 8.91 (br, NH2), 7.38 and 7.31 (d, 3J H-H ) ca. 7.7,
3
H4 & H7), 7.28 and 7.17 (t, J H-H ) ca. 6, H5 & H6), 6.30 (s,
3
H2), 3.23 (s, H1), 3.00 (m, CH2N), 2.6-2.4 (m, IndCH2CH2),
3J H-H ) 7.4, H4 & H7), 7.30 and 7.20 (t, J H-H ) 7.3, H5 &
1.48 (s, C(CH3)3). 13C{1H} NMR of the HBr salt (CDCl3): δ
H6), 6.22 (s, H2), 4.83 (s, NH2), 3.33 (s, H1), 2.80 (t, J H-H
)
3

1512 Organometallics, Vol. 19, No. 8, 2000
Groux et al.
3
3
7.0, CH2N), 2.60 (t, J H-H ) 7.0, Ind-CH2), 1.85 (quint, J H-H
) 7.3, IndCH2CH2). 13C{1H} NMR (CDCl3): δ 145.3 & 144.4
& 143.9 (C3a, C7a, C3), 127.8, 125.9, 124.4, 123.7 (C4-7),
118.8 (C2), 42.0 (CH2NH2), 37.6 (C1), 31.9 (IndCH2), 25.0
(CH2CH2CH2). Anal. Calcd for C12H15N‚HBr: C, 56.71; H, 6.34;
N, 5.51. Found: C, 56.64; H, 6.40; N, 5.47.
(η3:η0-In d (CH2)3NMe2)Ni(P P h 3)Cl (10). An Et2O solution
(70 mL) containing 5 (802 mg, 3.98 mmol) and BuLi (1.60 mL
of a 2.5 M solution in hexane) was stirred for 16 h and then
transferred (dropwise over 3 h) to a stirred slurry of (PPh3)2-
NiCl2 (3.90 g, 6.0 mmol) in Et2O (30 mL). Filtration of the
resulting wine red mixture followed by evaporation gave the
desired product as a red solid (1.90 g, ca. 85% crude yield)
which also contained some PPh3 and Ph3PdO. Repeated
recrystallizations with CH2Cl2/hexane failed to yield analyti-
cally pure samples because of the formation of what appears
to be a polymeric material (see Results and Discussion). 1H
NMR of crude solid (DMSO-d6): δ 7.7-7.2 (m, aromatic
protons of PPh3 and Ind), 7.06 (s), 6.92 (t, J ) 6.0), 6.74 (d, J
) 7.2), 4.13 (s), 2.33 and 2.19 (s, NMe2), 1.9-1.4 (m,
CH2CH2CH2). 31P{1H} NMR (DMSO-d6): δ 30.9 (s).
(η3:η0-In d (CH2)3N(t-Bu )H)Ni(P P h 3)Cl (7). The mixture of
1‚HBr (1.07 g, 3.45 mmol) and BuLi (2.76 mL of a 2.5 M
solution in hexane, 6.90 mmol) in Et2O (200 mL) was stirred
for 16 h at room temperature and then transferred (dropwise
over 2 h) to the stirred suspension of (PPh3)2NiCl2 (2.93 g, 4.49
mmol) in Et2O (50 mL). The final mixture was stirred for a
further 30 min after the addition was complete and then
filtered and evaporated. The solid residue was then dissolved
in CH2Cl2 (ca. 15 mL), diluted with hexane (ca. 200 mL), and
cooled to give the desired product as a dark red solid (1.27 g,
63%). 1H NMR (C6D6): δ 7.64 and 6.97 (m, PPh3), 7.24 (d, 3J H-H
Rea ction of Li[In d CH2CH2NHCH2P h ] w ith (P P h 3)2-
NiCl2. Slow addition of an Et2O solution (30 mL) of Li[3] (152
mg, 0.57 mmol) to the stirred slurry of (PPh3)2NiCl2 (373 mg,
0.57 mmol) in Et2O (30 mL) led to the formation of a reddish
color characteristic of the complexes IndNi(PPh3)Cl. The red
color turned brown over a few minutes, and a brown powder
precipitated. Both the filtrate and the solid were analyzed by
NMR spectroscopy: the 31P{1H} spectra showed no peaks
3
3
) 7.7, H7), 7.10 (t, J H-H ) 7.4, H6), 6.84 (t, J H-H ) 7.4, H5),
3
6.54 (s, H2), 6.18 (d, J H-H ) 7.7, H4), 3.47 (s, H3), 2.70 and
2.35-2.13 (br m, IndCH2CH2CH2) 1.10 (s, t-Bu). 13C{1H} NMR
(CDCl3): δ 134.2 (d, 2J P-C ) 11.4, o-C), 134.0 (C3a/C7a), 132.0
3
(d, J P-C ) 43.9, i-C), 130.2 (p-C), 128.1 (d, J P-C ) 10.1, m-C),
125.6 & 126.1 (C5 & C6), 118.2 & 116.7 (C4 & C7), 105.9 (C1),
102.1 (s, C2), 69.3 (s, C3), 53.3 (NCMe3), 42.6 (CH2N), 28.9
(Me), 28.5 (IndCH2), 23.2 (s, CH2CH2CH2). 31P{1H} NMR
(C6D6): δ 33.6. The missing signal for C3a/C7a is presumably
1
except for free PPh3, and the H spectra contained very broad,
featureless peaks. Repeating the reaction at -50 °C did not
yield a tractable product.
obscured by the other aromatic signals. Anal. Calcd for C34H37
ClNNiP‚CH2Cl2: C, 62.77; H, 5.87; N, 2.09. Found: C, 62.84;
H, 5.44; N, 1.62.
(η3:η0-In d (CH2)4N(t-Bu )H)Ni(P P h 3)Cl (8). The above pro-
cedure for 7 was repeated using 2‚HBr to yield 419 mg of the
crude product (46%). 1H NMR (C6D6): δ 7.62 and 6.98 (m, PPh3
-
Rea ction of Li[In d (CH2)3NH2] w ith (P P h 3)2NiCl2. Stir-
ring an Et2O (100 mL) mixture containing 6‚HBr (500 mg, 1.97
mmol) and BuLi (1.57 mL of a 2.5 M solution in hexane) for 1
h, followed by slow addition to the stirred slurry of (PPh3)2-
NiCl2 (1.93 g, 2.95 mmol) in Et2O (30 mL) led to the formation
of a dark red color. Filtration and evaporation of the solvent
gave a dark solid (1.05 g) which was analyzed by NMR
spectroscopy: the 31P{1H} NMR spectrum contained a signal
attributable to free PPh3, while the 1H NMR spectrum
contained only broad, featureless peaks.
3
3
and H6), 7.22 (d, J H-H ) ca. 7, H7), 6.85 (t, J H-H ) ca. 7,
H5), 6.37 (s, H2), 6.12 (d, J H-H ) 7.2, H4), 3.58 (s, H3), 2.54
3
(br, CH2N), 2.43 & 2.19 (br, IndCH2), 1.96 & 1.86 (br,
IndCH2CH2), 1.62 (br, IndCH2CH2CH2), 1.05 (s, t-Bu), 0.41 (br,
NH). 13C{1H} NMR (C6D6): δ 134.7 (d, J P-C ) 10.8, o-C),
2
Reaction of Li2[In dCH2CH2NCH2P h ] with (P P h 3)2NiCl2.
The mixture of 3‚HCl (250 mg, 0.83 mmol) and 3 equiv of BuLi
(1.0 mL of a 2.5 M solution in hexane) was stirred in Et2O (30
mL) for 16 h and added dropwise to the suspension of (PPh3)2-
NiCl2 (818 mg, 1.25 mmol) in Et2O (30 mL). The resulting red-
brown mixture was filtered to remove the residual solids,
evaporated, and analyzed by NMR spectroscopy. The 31P{1H}
NMR spectrum showed only a peak corresponding to free PPh3,
while the 1H NMR spectrum contained broad, featureless
peaks.
133.0?? (C3a/C7a), 133.0 (d, J P-C ) 43.8, i-C), 130.2 (p-C), 128.1
(d, J P-C ) 10.1, m-C), 126.6 & 126.1 (s, C5 & C6), 119.0 &
3
116.9 (s, C4 & C7), 106.8 (s, C1), 102.4 (s, C2), 69.5 (s, C3),
50.0 (NCMe3), 42.6 (CH2N), 29.3 (Me), 27.5 (IndCH2), 25.2 &
23.0 (s, IndCH2CH2CH2). The signal for m-C of PPh3 is
obscured by the solvent peak at 128 ppm. 31P{1H} NMR
(C6D6): δ 33.5 (s). Anal. Calcd for C35H39ClNNiP: C, 70.20;
H, 6.56; N, 2.34. Found: C, 70.02; H, 6.78; N, 2.22.
(η3:η0-In d (CH2)2NMe2)Ni(P P h 3)Cl (9). An Et2O solution
(200 mL) containing 4 (500 mg, 2.67 mmol) and BuLi (1.08
mL of a 2.5 M solution in hexane) was stirred for 30 min and
then transferred (dropwise over 4 h) to a stirred slurry of
(PPh3)2NiCl2 (2.62 g, 4.0 mmol) in Et2O (20 mL). Evaporation
of the resulting red mixture gave a reddish solid which was
extracted with hexane (3 × 50 mL), concentrated, and cooled.
Filtration of the cold mixture gave a first crop of the desired
product (ca. 800 mg of a reddish solid) which was found to
contain some PPh3 and Ph3PdO. Addition of hexane to the
filtrate and cooling gave ca. 300 mg of a red solid. Microcrystals
suitable for X-ray analysis were obtained by repeated recrys-
tallization of the combined solids in Et2O/hexane and cyclo-
hexane/hexane. 1H NMR (C6D6): δ 7.63 and 6.99 (m, PPh3),
[(η3:η1-In d (CH2)2NMe2)Ni(P P h 3)]+ (11). To a CH2Cl2 solu-
tion (ca. 30 mL) of complex 9 (110 mg, 0.20 mmol) at room
temperature was added NaBPh4 (478 mg, 1.40 mmo), and the
mixture was stirred for 1 h. Filtration of the mixture followed
by washing with CH2Cl2 allowed the removal of the excess
NaBPh4 (solid); evaporation of the filtrate gave a reddish solid
1
(ca. 100 mg, 60%). H NMR (CDCl3): δ 7.7-7.1 (m, aromatic
signals of PPh3, [BPh4]-, and H5, H6, and H7 of Ind), 6.78 (s,
3
H2), 5.54 (d, J H-H ) 7.8, H4), 3.94 (s, H3), 2.62 (m, IndCH2),
1.73 (m, CH2NMe2), 1.67 (s, NMe), 1.30 (s, NMe). 13C{1H} NMR
(CDCl3): δ 164.5 (4-line multiplet, J B-C ) 50, i-C of BPh4),
136.9 (m-C of BPh4), 134.1 (d, 2J P-C ) 11.9, o-C of PPh3), 132.2
(p-C of PPh3), 129.9 (d, 2J P-C ) 9.9, m-C of PPh3), 131.1 & 125.5
(C3a/C7a), 129.0 & 128.4 (C5/C6), 126.3 (o-C of BPh4), 122.5
3
3
7.22 (d, J H-H ) 7.3, H7), 7.10 (t, J H-H ) 7.4, H6), 6.84 (t,
3J H-H ) 7.4, H5), 6.70 (s, H2), 6.11 (d, J H-H ) 7.3, H4), 3.42
3
3
(p-C of BPh4), 119.0 & 118.7 (C4/C7), 109.8 (d, J P-C ) 11.8,
(s, H3), 2.89 and 2.74 (br, CH2N), 2.40 and 2.16 (br, IndCH2),
2.23 (br, NMe2). 13C{1H} NMR (toluene-d8, 208 K): δ 134.4
C1), 108.2 (C2), 76.3 (CH2N), 70.2 (C3), 51.5 (NMe), 24.3
(IndCH2). 31P{1H} NMR (CDCl3): δ 29.1 (s). Anal. Calcd for
2
(d, J P-C ) 11.5, o-C), 132.2 (d, J P-C ) 43.2, i-C), 130.3 (p-C),
C
55H51BNNiP: C, 79.93; H, 6.22; N, 1.69. Found: C, 79.64; H,
126.4 & 126.1 (C5 & C6), 118.3 & 116.4 (C4 & C7), 105.3 (d,
2J P-C ) ca. 10, C1), 103.7 (C2), 66.9 (C3), 56.8 (CH2N), 45.6
(Ni-Me), 24.6 (IndCH2); the signals corresponding to m-C of
PPh3 and C3a and C7a of the Ind are obscured by the solvent
resonances. 31P{1H} NMR (C6D6): δ 30.8 (s). Anal. Calcd for
6.54; N, 1.56.
[(η3:η1-In d (CH2)3NMe2)Ni(P P h 3)]+ (12). To a CH2Cl2 solu-
tion (ca. 30 mL) of complex 10 (112 mg, 0.20 mmol) at room
temperature was added NaBPh4 (342 mg, 1.00 mmol), and the
mixture was stirred for 1 h. Filtration of the mixture followed
by washings with CH2Cl2 allowed the removal of the excess
C
31H31ClNNiP: C, 68.61; H, 5.76; N, 2.58. Found: C, 68.01;
H, 5.72; N, 2.40.

Nickel Complexes with η-Indenyl Ligands
Organometallics, Vol. 19, No. 8, 2000 1513
Ta ble 1. X-r a y Cr ysta llogr a p h ic Da ta for 7 a n d 9
SHELXS96 and difmap synthesis using SHELXL96; refine-
ments were done on F2 by full-matrix least squares. The
disorder observed in the positions of the solvent molecule and
the t-Bu group in 7 is responsible for the relatively high R
value of 8.2%. The occupancy factors for these groups were
refined and in the last cycle fixed at 60% (for C12, C13, C14,
and C15 of the t-Bu group and C50, Cl51, and Cl52 of CH2Cl2)
and 40% (for C16, C17, C18, and C19 of the t-Bu group and
C60, Cl61, and Cl62 of CH2Cl2) over the two observed positions.
The atoms C12 and C16 are 0.088 Å apart; their thermal
parameters were kept identical and the carbon atoms C13-
C15 and C17-C19 as well as all the solvent atoms were refined
isotropically. No hydrogen bonding was found between N-H
and Cl atoms in 7. The CH2NMe2 moiety in 9 is also disordered
over two positions, but this does not have a significant impact
over the overall quality of the data obtained for this structure.
The ORTEP diagrams are shown in Figures 1 and 2, along
with selected bond distances and angles. Complete crystal-
lographic data for both structures are included in the Sup-
porting Information.
7
9
formula
mol wt
C34H37NiPNCl‚CH2Cl2 C31H31NiPNCl
669.73
542.72
cryst color
cryst habit
cryst dimens, mm
cell setting
space group
a, Å
orange-red
thin plate
0.43 × 0.15 × 0.07
triclinic
P1h
9.910(3)
10.383(12)
19.556(9)
90.24(6)
92.10(3)
115.72(4)
1680(2)
dark red
block
0.29 × 0.11 × 0.07
triclinic
P1h
9.215(2)
10.228(4)
16.250(6)
76.60(3)
87.94(2)
65.43(2)
1351.8(8)
2
b, Å
c, Å
R, deg
â, deg
γ, deg
V, Å3
Z
2
D(calcd), g cm-3
λ(Cu KR), cm-1
temp, K
1.3324
1.540 56
293(2)
1.3333
1.540 56
293(2)
diffractometer
2θmax, deg
Nonius CAD-4
140.0
Nonius CAD-4
140.0
ω/2θ scan
5137
data collecn method ω/2θ scan
no. of rflns used
(I > 2σ(I))
R, Rw
6366
Ack n ow led gm en t. We are grateful to the NSERC
of Canada, the FCAR of Que´bec, and Universite´ de
Montre´al for financial support.
0.0820, 0.2346
0.0509, 0.1007
NaBPh4 (solid); evaporation of the filtrate gave a reddish solid
(ca. 110 mg, 65%). 31P{1H} NMR (CDCl3): δ 26.9 (s).
Su p p or tin g In for m a tion Ava ila ble: Complete details on
the X-ray analyses of 7 and 9, including tables of bond
distances and angles, anisotropic thermal parameters, and
hydrogen atom coordinates. This material is available free of
charge via the Internet at http://pubs.acs.org.
X-r a y Diffr a ction Stu d ies of 7 a n d 9. Orange-red crystals
of 7 were grown from CH2Cl2/hexane at -20 °C; complex 7
cocrystallizes with one molecule of CH2Cl2 in each unit cell.
Dark red crystals of 9 were grown from Et2O/hexane at room
temperature. Crystallographic data for 7 and 9 are collected
in Table 1. The structures were solved by direct methods using
OM9907122