Zirconium complexes involving 2-phosphorus-substituted indenyl fragments

Article abstract of DOI:10.1021/om050236h

A series of 2-R₂P-substituted indenes, where R₂P = Ph₂P, Cy₂P, ⁱPr₂P, and ^tBu(H)P, were obtained via Pd-catalyzed reactions of 2-bromo-1H-indene (or 1H-inden-2-yl trifluoromethane sulfonate) with R ₂PH/Et₃N. Analogous indenes bearing Me₂P, ^tBu(Cl)P, and ^tBu₂P substituants at position 2 were obtained through the reaction of 1H-inden-2-ylphosphonous dichloride with MeLi, ^tBuMgCl, and ^tBuMgCl/^tBuLi-CuCN, respectively. Diethyl 1H-inden-2-ylphosphonate, prepared via the Ni-catalyzed Arbuzov reaction of 2-bromo-1H-indene with P(OEt)₃, was found to be a convenient starting material for the synthesis of 2-H₂P-substituted indene. 1H-Inden-2-yl(phenyl)phosphine, prepared via the Pd-catalyzed arylation of 2-H₂P-substituted indene by PhI, turned out to react with 2-bromo-1H-indene in the presence of Pd(PPh₃)₄ and Et ₃N to form di(1H-inden-2-yl)(phenyl)phosphine in almost quantitative yield. Analogously, di(1H-inden-2-yl)(tert-butyl)phosphine was prepared via catalytic reaction of ^tBuPH₂ with 2 equiv of 2-bromo-1H-indene. Triethylamine-promoted condensation of indenes bearing P(H)^tBu and P(Cl)^tBu fragments gave a mixture of cis- and trans-bis-indenyldiphosphines. Zirconium complexes (2-R₂P-indenyl) ₂ZrCl₂ (R₂P = Ph₂P, Me₂P, Cy₂P, ⁱPr₂P, ^tBu₂P), as well as ansa-zirconocenes RP(2-indenyl)₂ZrCl₂ (R = Ph, ^tBu), were obtained in good yields from ZrCl₄(THF) ₂ and lithium salts of the respective 2-P-substituted indenes. Ansa-zirconocene (^tBuP)₂(2-indenyl)₂ZrCl ₂ including a P₂R₂ bridge was synthesized in a similar manner and isolated as the pure rac-isomer.

Full text of DOI:10.1021/om050236h

3024
Organometallics 2005, 24, 3024-3035
Zirconium Complexes Involving
2-Phosphorus-Substituted Indenyl Fragments
Denis N. Kazul’kin,† Alexey N. Ryabov,† Vyatcheslav V. Izmer,†
Andrei V. Churakov,‡ Irina P. Beletskaya,† Carol J. Burns,§ and
Alexander Z. Voskoboynikov*,†
Department of Chemistry, Moscow State University, Leninskie Gory, GSP-2, Moscow,
119992, Russian Federation, N. S. Kurnakov Institute of General and Inorganic Chemistry, 31
Leninsky Avenue, Moscow, 119991, Russian Federation, and Los Alamos National Laboratory,
Chemical Division MS J515, Los Alamos, New Mexico 87545
Received March 29, 2005
A series of 2-R2P-substituted indenes, where R2P ) Ph2P, Cy2P, iPr2P, and tBu(H)P, were
obtained via Pd-catalyzed reactions of 2-bromo-1H-indene (or 1H-inden-2-yl trifluoromethane
t
t
sulfonate) with R2PH/Et3N. Analogous indenes bearing Me2P, Bu(Cl)P, and Bu2P substit-
uents at position 2 were obtained through the reaction of 1H-inden-2-ylphosphonous
dichloride with MeLi, tBuMgCl, and tBuMgCl/tBuLi-CuCN, respectively. Diethyl 1H-inden-
2-ylphosphonate, prepared via the Ni-catalyzed Arbuzov reaction of 2-bromo-1H-indene with
P(OEt)3, was found to be a convenient starting material for the synthesis of 2-H2P-substituted
indene. 1H-Inden-2-yl(phenyl)phosphine, prepared via the Pd-catalyzed arylation of 2-H2P-
substituted indene by PhI, turned out to react with 2-bromo-1H-indene in the presence of
Pd(PPh3)4 and Et3N to form di(1H-inden-2-yl)(phenyl)phosphine in almost quantitative yield.
Analogously, di(1H-inden-2-yl)(tert-butyl)phosphine was prepared via catalytic reaction of
tBuPH2 with 2 equiv of 2-bromo-1H-indene. Triethylamine-promoted condensation of indenes
bearing P(H)tBu and P(Cl)tBu fragments gave a mixture of cis- and trans-bis-indenyldiphos-
phines. Zirconium complexes (2-R2P-indenyl)2ZrCl2 (R2P ) Ph2P, Me2P, Cy2P, iPr2P, tBu2P),
as well as ansa-zirconocenes RP(2-indenyl)2ZrCl2 (R ) Ph, tBu), were obtained in good yields
from ZrCl4(THF)2 and lithium salts of the respective 2-P-substituted indenes. Ansa-
zirconocene (tBuP)2(2-indenyl)2ZrCl2 including a P2R2 bridge was synthesized in a similar
manner and isolated as the pure rac-isomer.
Introduction
However, the synthesis of the respective indenyl ligands
via the reaction of indenyllithium salts with organo-
phosphorus(III) halides has some limitations. Only
isomeric 1(3)-P-substituted indenes can be obtained in
this manner,5 while 2-alkyl(aryl)phosphino-substituted
analogues are still inaccessible. Although analogous
2-aminoindenes can be readily obtained via simple
condensation of indanone-2 with nucleophilic secondary
amines (see, e.g., ref 6 and synthesis of the correspond-
ing zirconocenes7), the respective indenylphosphines
cannot be prepared in this manner. The only known
pathway8 to 2-P-substituted indenes, described by
For the last two decades, the chemistry of group 4
metallocenes has exhibited a vigorous growth because
of the outstanding catalytic properties of these com-
pounds in olefin polymerization.1 Zirconium complexes
bearing more electron-rich cyclopentadienyl (indenyl,
fluorenyl) ligands were shown to possess higher catalytic
activity.2 At the same time, well-designed metallocene
precursors involving substituents and/or bridges in
definite positions of cyclopentadienyl (indenyl, fluorenyl)
fragments can result in highly stereospecific polymer-
ization of propene and other R-olefins because of specific
space blocking of the cationic zirconium center.1,3,4 From
these points of view, metallocenes including electron-
rich organophosphorus(III) substituents in the cyclo-
pentadienyl ring could be of particular importance.
(5) (a) Schaverien, C. J.; Ernst, R.; Terlouw, W.; Schut, P.; Sud-
meijer, O.; Budzelaar, P. H. M. J. Mol. Catal. A 1998, 128, 245. (b)
Heuer, L.; Bode, U. K.; Jones, P. G.; Schmutzer, R. Z. Naturforsch., B
1989, 44, 1082. (c) Alt, H. G.; Jung, M. J. Organomet. Chem. 1998,
568, 127. (d) Fallis, K. A.; Anderson, G. K.; Rath, N. P. Organometallics
1992, 11, 885. (e) Stradiotto, M.; Kozak, C. M.; McGlinchey, M. J. J.
Organomet. Chem. 1998, 564, 101. (f) Starzevski, K. A. O.; Kelly, M.
W.; Stumpf, A.; Freitag, D. Angew. Chem., Int. Ed. 1999, 38, 2439. (g)
Adams, J. J.; Berry, D. E.; Browning, J.; Burth, D.; Curnow, O. J. J.
Organomet. Chem. 1999, 580, 245.
* To whom correspondence should be addressed. E-mail: voskoboy@
org.chem.msu.ru. Phone/fax: +7(095)939-4764.
† Moscow State University.
‡ N. S. Kurnakov Institute of General and Inorganic Chemistry.
§ Los Alamos National Laboratory.
(6) Edlund, U. Acta Chem. Scand. 1973, 27, 4027.
(1) Metallocenes: Synthesis, Reactivity, Applications; Togni, A.,
Halterman, R. L., Eds.; Wiley-VCH: New York, 1998.
(2) Squire, K. R. In Proceedings of the 222nd American Chemical
Society Meeting, Chicago, 2001.
(3) Brintzinger, H. H.; Fischer, D.; Mu¨lhaupt, R.; Rieger, B.;
Waymouth, R. M. Angew. Chem., Int. Ed. Engl. 1995, 34, 1143.
(4) Resconi, L.; Cavallo, L.; Fait, A.; Piemontesi, F. Chem. Rev. 2000,
100, 1253.
(7) Luttikhedde, H. J. G.; Leino, R. P.; Wilen, C.-E.; Na¨stman, J.
H.; Ahlgren, M. J.; Pakkanen, T. A. Organometallics 1996, 15, 3092.
(8) Zirconium-mediated synthesis of the well-designed 2-Ph2P-
substituted indenes 2-(diphenylphosphino)-N-[(trimethylsilyl)methyl]-
1H-inden-3-amine and N-(2,6-dimethylphenyl)-2-(diphenylphosphino)-
1H-inden-3-amine is described in: Cadierno, V.; Zablocka, M.;
Donnadieu, B.; Igau, A.; Majoral, J.-P.; Skowronska, A. J. Am. Chem.
Soc. 1999, 121, 11086.
10.1021/om050236h CCC: $30.25 © 2005 American Chemical Society
Publication on Web 05/11/2005

Zr Complexes with 2-R2P-Substituted Indenyl
Organometallics, Vol. 24, No. 12, 2005 3025
Scheme 1
Scheme 2
Scheme 3
Timokhin et al.,9 is based on the reaction of indene with
PCl5 followed by reduction of trichloro(1H-inden-2-yl)-
phosphonium hexachlorophosphate(1-) (1) by (EtO)2P-
(O)H in the presence of Et3N (Scheme 1). This method
results in pure 1H-inden-2-ylphosphonous dichloride,
which then can be transferred into the desired 2-dialkyl-
(aryl)phosphino-substituted indenes using nucleophilic
reagents, preferably with low basicity (see below) to
exclude side metalation of the indenyl fragment.
This paper is aimed at the development of selective
Pd-catalyzed and alternative routes to 2-alkyl(aryl)-
phosphino-substituted indenes, as well as synthesis and
characterization of zirconium complexes bearing these
ligands.
Scheme 4
Scheme 5
vinylphosphines requiring no preliminary synthesis of
silylphosphine starting materials. Vinyl halides11d,13 and
triflates13a,14 are known to react with Ph2PH in the
presence of Pd catalyst and base, such as trialkylamines
or K2CO3, to form the respective cross-coupling prod-
ucts.15 We found that this procedure can be applied for
the synthesis of 2-R2P-substituted indenes. Moreover,
in this reaction besides Ph2PH various dialkylphos-
phines can be used. In this way, the desired phosphi-
noindenes 3-5 were obtained in almost quantitative
yields in the presence of 4 mol % of Pd(PPh3)4 and Et3N
in toluene under reflux (Scheme 3). However, on the
evidence of 31P NMR spectroscopy, sterically strained
tBu2PH gave di(tert-butyl)(1H-inden-2-yl)phosphine (6)
in as low as 5% yield.
On the other hand, 1H-inden-2-yl trifluoromethane-
sulfonate was found to react readily with dicyclohexyl-
phosphine to form indene 5 in almost quantitative yield
(Scheme 4).
At the next stage of our research, we have found that,
alternatively, 1H-inden-2-ylphosphonous dichloride (2)
can be used to synthesize the desired 2-R2P-substituted
indenes. First, synthesis of 2 was improved; that is,
trichlorosilane was used instead of (EtO)2P(O)H to
reduce 1 (Scheme 1), so 2 was obtained in almost
quantitative yield. Phosphine 2 was found to react
readily with methyllithium in ether at -90 °C to give
dimethyl(1H-inden-2-yl)phosphine (7) in almost quan-
titative yield also (Scheme 5).
Results and Discussion
Synthesis of 2-R2P-Substituted Indenes (R )
Alkyl, Aryl, H). For the synthesis of 2-R2P-substituted
indenes, we developed several synthetic procedures
based on metal-catalyzed transformations of 2-bromo-
1H-indene, as well as reaction of 2 with Grignard and
organocopper reagents. Recently, Beletskaya and co-
workers have shown that Pd-catalyzed coupling of vinyl
bromides10 with Ph2PSiMe3 results in the respective
diphenylphosphinoethenes in good yield.11 We have
found that 2-bromo-1H-indene reacts with Ph2PSiMe3
in a manner similar to form 1H-inden-2-yl(diphenyl)-
phosphine (3) in 89% yield (on the evidence of NMR
spectroscopy) in the presence of 3 mol % of Pd(II)
complex in benzene under reflux (Scheme 2). This
colorless crystalline product was isolated in 65% yield
after crystallization from ethanol.
It should be noted that an attempt to synthesize 3
using the Grignard reagent derived from 2-bromo-1H-
indene failed.12 On the evidence of NMR spectroscopy,
this reaction with Ph2PCl in ether at 0 °C gives 3 in as
low as 6% yield along with ca. 70% of 1H-inden-3-yl-
(diphenyl)phosphine. Taking into account this failure,
we also applied an alternative catalytic approach to
(9) Timokhin, B. V.; Dmitriev, V. I.; Vengel’nikova, V. N.; Donskikh,
V. I.; Kalabina, A. V. Zh. Obshch. Khim. 1983, 52, 291.
Analogously, this starting material was successfully
(10) Analogous reactions applying arylhalides were described in: (a)
Tunney, S. E.; Stille, J. K. J. Org. Chem. 1987, 52, 748. (b) Beletskaya,
I. P.; Veits, Y. A.; Leksunkin, V. A.; Foss, V. L. Izv. Akad. Sci., Ser.
Khim. (Russ.) 1992, 1645. (c) Vets, Y. A.; Karlstedt, N. B.; Foss, V. L.;
Beletskaya, I. P. Zh. Org. Khim. (Russ.) 1998, 34, 559. (d) Bruuner,
H,; Janura, M. Synthesis 1998, 45.
used to obtain 6, which is practically unavailable via
t
cross-coupling reaction of 2-bromoindene with Bu2PH
(see above). In this way, 2 and 1 equiv of tBuMgCl gave
tert-butyl(1H-inden-2-yl)phosphinous chloride (8) and
then the desired di(tert-butyl)(1H-inden-2-yl)phosphine
applying the organocopper reagent (Scheme 6). The total
(11) (a) Veits, Y. A.; Karlstedt, N. B.; Beletskaya, I. P. Zh. Org.
Khim. 1994, 30, 66. (b) Veits, Y. A.; Karlstedt, N. B.; Nasonova, N. S.;
Borisenko, A. A.; Beletskaya, I. P. Zh. Org. Khim. 1994, 30, 481. (c)
Veits, Y. A.; Karlstedt, N. B.; Beletskaya, I. P. Tetrahedron Lett. 1995,
36, 4121. (d) Kazankova, M. A.; Chirkov, E. A.; Kochetkov, A. N.;
Efimova, I. V.; Beletskaya, I. P. Tetrahedron Lett. 1999, 40, 573.
(12) Analogous synthesis of 2-Me3Si-substituted indene and, then,
(2-Me3Si-indenyl)2ZrCl2, see: (a) Davison, A.; Rakita, P. E. J. Orga-
nomet. Chem. 1970, 23, 407. (b) Grimmer, N. E.; Coville, N. J.; de
Koning, C. B.; Smith, J. M.; Cook, L. M. J. Organomet. Chem. 2000,
616, 112, respectively.
(13) (a) Skoda-Fo¨ldes, R.; Banffy, L.; Horvath, J.; Tuba, Z.; Kollar,
L. Monatsh. Chem. 2000, 131, 1363. (b) Trostyanskaya, I. G.; Titskii,
D. Y.; Anufrieva, E. A.; Borisenko, A. A.; Kazankova, M. A.; Beletskaya,
I. P. Izv. Akad. Sci., Ser. Khim. (Russ.) 2001, 2003.
(14) (a) Lipshutz, B. H.; Buzard, D. J.; Yun, C. S. Tetrahedron Lett.
1999, 40, 201. (b) Gilbertson, S. R.; Fu, Z.; Starkey, G. W. Tetrahedron
Lett. 1999, 40, 8509.

3026 Organometallics, Vol. 24, No. 12, 2005
Kazul’kin et al.
Scheme 6
Scheme 7
Scheme 8
saturated P-P-P-C-C five-membered ring fused to a
five-membered ring of indane. It should be noted that
an alternative attempt to obtain 10, of importance for
ansa-metallocene synthesis (see below), via the reduc-
tion of 2 by LiAlH4 failed.
The molecular structure of 12 is shown in Figure 1.
In this structure, bond angles about phosphorus atoms
yield of 6 from 2 was 27%. It should be noted that an
alternative reaction of 2 with 2 equiv of Grignard or
organolithium reagent resulted in very low yield of the
desired products (6 and 7) because of side metalation
of the indenyl fragment.
The other promising pathway to 2-R2P-substituted
indenes seems to be a NiCl2-catalyzed Arbuzov reaction
giving dialkyl vinylphosphonates from vinylbromides
and trialkyl phosphites.16 In this manner, we succeeded
in the preparation of diethyl 1H-inden-2-ylphosphonate
(9)17 (Scheme 7), which was isolated in 75% yield as a
yellowish oil.
Figure 1. Crystal structure of 12. Displacement ellipsoids
are shown at the 50% probability level. Selected bond
lengths (Å) are P(1)-C(21) 1.819(5), P(1)-P(3) 2.205(2),
P(1)-P(2) 2.211(2), P(2)-C(11) 1.805(4), P(2)-C(2)
1.879(4), P(3)-C(1) 1.864(4), P(3)-H(3) 1.30(3), C(1)-C(9)
1.537(8), C(1)-C(2) 1.568(6), C(1)-H(1) 0.96(4), C(2)-C(3)
1.497(6), C(2)-H(2) 1.04(4).
range within 87(2)-104.2(2)°. The P-P distances
(2.205(2), 2.211(2) Å) are close to their ordinary value,
2.214 Å.18 The P(2)-C(2) and P(3)-C(1) bond lengths
(1.879(4) and 1.864(4) Å) are noticeably longer than
P(1)-C(21) and P(2)-C(11) (1.819(5) and 1.805(4) Å)
due to the different hybridization states of the carbon
atoms involved (sp3 and sp2, respectively). All three
inde(a)nyl fragments are planar within 0.05 Å.
Reaction of phosphonate 9 with 2 equiv of MeLi in
ether followed by reduction by trichlorosilane gave
dimethyl(1H-inden-2-yl)phosphine (7) in 29% total yield
(Scheme 9). Thus, this synthetic pathway is inferior to
Phosphonate 9 was reduced by an excess of LiAlH4
in ether to give primary phosphine 10 (Scheme 8). The
crude product distilled in vacuo was found to be a ca.
4:1 mixture of 1H-inden-2-ylphosphine (10) and 2,3-
dihydro-1H-inden-2-ylphosphine (11). A careful frac-
tional distillation of this mixture resulted in 10 of 93%
purity, which was further used without additional
purification. The overall yield of phosphines 10 and 11
was ca. 63%, so we decided to study other products of
this reaction. One of them was isolated in 7% yield as a
colorless crystalline solid using low-temperature crys-
tallization from ether. This unusual compound 12
(Scheme 8), which was characterized by NMR spectros-
copy and X-ray crystal structure analysis, includes a
Scheme 9
(15) (a) Herd, O.; Hessler, A.; Hingst, M.; Tepper, M.; Stelzer, O. J.
Organomet. Chem. 1996, 522, 69. (b) Herd, O.; Hessler, A.; Hingst,
M.; Machnitzki, P.; Tepper, M.; Stelzer, O. Catal. Today 1998, 42, 413.
(c) Machnitzki, P.; Nickel, T.; Stelzer, O.; Landgrafe, C. Eur. J. Inorg.
Chem. 1998, 1029. (d) Hillhouse, J. H.; Depalo, M. WO Patent
Application 0069866 for Cytec Technology Corp. (e) Hessler, A.;
Kottsieper, K. W.; Schenk, S.; Tepper, M.; Stelzer, O. Z. Naturforsch.,
B: Chem. Sci. 2001, 56, 347. (f) Brauer, D. J.; Hingst, M.; Kottsieper,
K. W.; Liek, Ch.; Nickel, T.; Tepper, M.; Stelzer, O.; Sheldrick, W. S.
J. Organomet. Chem. 2002, 645, 14. (g) Hillhouse, J. H. WO Patent
Application 0192276 for Cytec Technology Corp. (h) Hesser, A.; Stelzer,
O. J. Org. Chem. 1997, 62, 2362. (i) Kumobayashi, H.; Miura, T.; Sayo,
N.; Saito, T.; Zhang, X. Synlett 2001, 1055. (k) Birdsall, D. J.; Hope,
E. G.; Suart, A. M.; Chen, N.; Hu, Y.; Xiao, J. Tetrahedron Lett. 2001,
42, 8551. (l) Kraatz, H.-B.; Pletsch, A. Tetrahydron: Asymmetry 2000,
11, 1617, and references therein.
(16) (a) Tavs, P.; Weitkamp, H. Tetrahedron 1970, 26, 5529. (b)
Honig, M. L.; Martin, D. M. Phosphorus 1974, 4, 63. (c) Tavs, P. Chem.
Ber. 1970, 103, 2428. (d) Maier, L. Phosphorus 1973, 3, 19.
(17) Synthesis of this phosphonate can be also achieved by alco-
holysis of trichloro(1H-inden-2-yl)phosphonium hexachlorophosphate-
(1-) resulting from the reaction between indene and PCl5 as described
in: Pieroni, O. I.; Rodriguez, N. M.; Vuano, B. M.; Cabaleiro, M. C. J.
Chem. Res., Synop. 1993, 22.
the procedure using 2 and methylcuprate as starting
materials (see above). The intermediate product, 1H-
inden-2-yl(dimethyl)phosphine oxide (13), in the form
of its HCl-H2O solvate, was characterized by X-ray
crystal structure analysis (Figure 2). The indenyl frag-
ment of this compound is planar within 0.008 Å. The
phosphorus atom lies on the indenyl plane (the sum of
bond angles at carbon atom C(8) is 360.0°) and has a
distorted tetrahedral configuration due to the formation
by the hydroxyl group of a hydrogen bond with a solvate
water molecule. In this hydrogen bond, the water
molecule takes part as the acceptor, but it also forms
(18) Allen, F. H.; Kennard, O.; Watson, D. G.; Brammer, L.; Orpen,
A. G.; Taylor, R. J. Chem. Soc., Perkin Trans. 2 1987, S1.

Zr Complexes with 2-R2P-Substituted Indenyl
Organometallics, Vol. 24, No. 12, 2005 3027
Scheme 11
Scheme 12
Figure 2. Crystal structure of 13‚HCl‚H2O (ellipsoids are
drawn at the 50% probability level); hydrogen bonds are
shown by dotted lines. Selected bond lengths (Å) are P(1)-
O(1) 1.5439(12), P(1)-C(8) 1.7634(14), P(1)-C(11)
1.7775(16), P(1)-C(10) 1.7784(15), O(1)-H(1O) 0.90(4),
C(1)-C(9) 1.5023(19), C(5)-C(6) 1.3969(19), C(6)-C(7)
1.4556(19), C(7)-C(8) 1.3523(19), C(8)-C(9) 1.5097(18).
Scheme 13
Scheme 10
PhP(SiMe3)2, turned out to not react with 2-bromo-1H-
indene in the presence of Pd(PPh3)4, PdCl2(MeCN)2, or
Ni(acac)2.19 On the other hand, we found that 10 is a
good starting material for the synthesis of 1H-inden-2-
yl(phenyl)phosphine (17). The arylation of 10 with PhI
in the presence of 5 mol % of Pd(PPh3)4 and Et3N gave
17 in 95% yield (Scheme 11).
To develop a less time-consuming procedure for
synthesizing secondary phosphine 17, we studied the
reaction of indanone-2 with PhP(SiMe3)Li. Von Becker
et al. have shown that analogous reaction of lithium
salts of trimethylsilylphosphines with ketones followed
by treatment with Me3SiCl gives thermodynamically
unstable methylidenephosphines.20 We found that the
only phosphorus-containing product of the similar reac-
tion of indanone-2 was secondary phosphine 17 (Scheme
12), which on the evidence of 31P NMR spectroscopy was
formed in as low as 10% yield, probably via rearrange-
ment of unstable 1,3-dihydro-2H-inden-2-ylidene-
(phenyl)phosphine. This low yield for the unoptimized
procedure seems to result from slow addition of PhP-
(SiMe3)Li to indanone-2.
Next, the secondary phosphine 17 was found to react
with 2-bromo-1H-indene in the presence of 5 mol % of
Pd(PPh3)4 and Et3N under reflux (Scheme 13). This Pd-
catalyzed vinylation of the P-H bond of 17 gave the
desired phosphine 16 in almost quantitative yield (31P
NMR). Analytically pure product was isolated in 58%
yield after crystallization from ethanol.
One more bis-indenyl ligand bearing a diphosphine
fragment in position 2 that is of interest for ansa-
metallocene synthesis was obtained using the well-
known triethylamine-promoted condensation of P-H
and P-Cl substrates.21 In this way, diphosphine 18 was
obtained in 51% yield from 8 and 14 (Scheme 14). On
the evidence of NMR spectroscopy, this product consists
two hydrogen bonds with two chlorine anions as the
donor.
Thus, phosphonate 9 is a good starting material for
obtaining primary indenylphosphine 10, of importance
for synthesizing further bridging indenyl ligands (see
below).
Synthesis of Di(indenyl)phosphines. Actually,
synthesis of alkyl- and aryldi(indenyl)phosphines can
be achieved using metal-catalyzed reactions of 2 equiv
of 2-bromo-1H-indene with primary phosphines. No
examples of similar reactions with vinyl halides have
been described so far. Moreover, the respective Pd-
catalyzed reactions of primary phosphines with aryl
halides proceed slowly and were only applied either for
aryliodides15a-f or primary alkylphosphines.15g
t
In this study, we found that BuPH2 reacts readily
with 2-bromo-1H-indene in the presence of 5 mol % of
Pd(PPh3)4 and Et3N to form both mono- and disubsti-
tution products in a ratio that depends strongly on the
reagent ratio used (Scheme 10). On the evidence of 31
P
NMR spectroscopy, tert-butyl(1H-inden-2-yl)phosphine
(14) was formed in 79% yield for a 1 to 1.1 ratio of
2-bromo-1H-indene to the primary phosphine, whereas
tert-butyl[di(1H-inden-2-yl)]phosphine (15) was formed
in 21% yield in this case. The secondary phosphine 14
was isolated using fractional distillation in 31% yield
only, probably because of its partial decomposition
during the distillation. Alternatively, 2 equiv of 2-bromo-
t
1H-indene and BuPH2 gave 15 in almost quantitative
yield (31P NMR). In this case, tert-butyl[di(1H-inden-2-
yl)]phosphine was isolated in 85% yield in analytically
pure form.
For the synthesis of the analogous compound involv-
ing a PPh fragment, i.e., di(1H-inden-2-yl)(phenyl)-
phosphine (16), we used the alternative approach. The
reason for this decision was that, unfortunately, primary
aryl(vinyl) phosphines and the respective TMS deriva-
tives, such as PhPH2, phosphine 10, PhP(H)SiMe3, and
(19) A formation of traces of both 16 and 17 was detected by NMR
spectroscopy in the case of PhPH2 and PhP(H)SiMe3.
(20) von Becker, G.; Uhl, W.; Wessely, H. J. Z. Anorg. Allg. Chem.
1981, 479, 41.
(21) (a) Kuchen, W.; Buchwald, H. Chem. Ber. 1958, 91, 2871. (b)
Inorganic reactions and methods; Zuckerman, J. J., Ed.; VCH: New
York, 1988; Vol. 7, p 17; and references therein.

3028 Organometallics, Vol. 24, No. 12, 2005
Kazul’kin et al.
Scheme 14
Scheme 15
of two isomers, i.e., d-/l- and meso-1,2-di-tert-butyl-1,2-
di(1H-inden-2-yl)diphosphines. This seems to result
from the known hindered inversion at phosphorus in
phosphines.22
Figure 3. Crystal structure of 22. Displacement ellipsoids
are shown at the 50% probability level. Hydrogen atoms
are omitted for clarity. Selected bond lengths (Å) are
Zr(1)-Cl(1) 2.4132(7), Zr(1)-Cl(2) 2.4178(7), Zr(1)-C(1)
2.518(2), Zr(1)-C(2) 2.455(2), Zr(1)-C(3) 2.562(2), Zr(1)-
C(8) 2.610(2), Zr(1)-C(9) 2.554(2), Zr(1)-C(10) 2.543(2),
Zr(1)-C(11) 2.472(3), Zr(1)-C(12) 2.578(2), Zr(1)-C(17)
2.594(2), Zr(1)-C(18) 2.560(2), P(1)-C(1) 1.838(2), P(1)-
C(19) 1.873(3), P(1)-C(25) 1.866(2), P(2)-C(10) 1.836(3),
P(2)-C(31) 1.862(3), P(2)-C(37) 1.86(2), P(2)-C(37′)
1.900(17).
Synthesis and Molecular Structures of Zir-
conocenes. Zirconocenes 19-23 bearing 2-R2P-substi-
tuted indenyl ligands were obtained using the exchange
reaction between ZrCl4(THF)2 and the respective lithium-
indenyls in ether (Scheme 15). Complexes 19 and 22
were precipitated from saturated toluene solutions on
addition of hexanes and isolated in 58 and 47% yields,
respectively. Crystals of zirconocene 21 were obtained
in 43% yield from ether solution at -30 °C. Analogously,
zirconocenes 20 and 23 bearing PMe2 and PtBu2 frag-
ments were isolated in 61 and 64% yields using low-
temperature crystallization from toluene-hexanes and
toluene, respectively.
Scheme 16
Zirconium complex 22 bearing Cy2P substituents was
characterized by X-ray crystal structure analysis (Figure
3). The zirconium atom of this molecule has a distorted
pseudotetrahedral coordination, with the distances to
the centers of the cyclopentadienyl rings being 2.234(1)
and 2.243(1) Å, respectively. The angle Cp1-Zr(1)-Cp2
is 132.0(1)°. The Zr-Cl bond lengths (2.4132(7) and
2.4178(7) Å) are close to their ordinary value.23 The
phosphorus atoms are trigonal-pyramidal with stereo-
chemically active lone pairs. The indenyl fragments are
planar within 0.026 Å. The angle between the indenyl
planes is 55.5°, and the angle Cp1-Zr(1)-Cp2 is 132.0°.
The five-membered cycles of the indenyl fragments are
disposed in the staggered conformation with respect to
each other. The phosphorus atoms lie on the indenyl
planes (the sums of the bond angles at carbon atoms
C(1) and C(10) are 359.5° and 360.0°, respectively),
which indicates the absence of geometric strains in
ligands. The cyclohexyl substituents have the chair
conformation. The molecule 22 has the intrinsic sym-
metry C2 (a 2-fold axis passes through the Zr(1) atom
and the middle of the Cl(1)‚‚‚Cl(2) length), which is not
realized in the crystal (space group P1h).
Scheme 17
crystalline solid through low-temperature crystallization
from toluene.
Ansa-zirconocenes 25 and 26 of Cs symmetry includ-
ing RP bridges in position 2 of indenyls24 were prepared
from ZrCl4(THF)2 and dilithium salts of 15 and 16,
respectively (Scheme 17). The complexes were isolated
in analytically pure form in 56 and 36% yields by low-
temperature crystallization from toluene and toluene-
hexanes, respectively.
t
Ansa-zirconocene 25, including a BuP bridge, was
characterized by X-ray crystal structure analysis (Figure
4). The zirconium atom has a distorted pseudotetra-
hedral coordination, with the distances to the centers
of the cyclopentadienyl rings being 2.225(1) and
2.219(1) Å, respectively. The Zr-Cl bond lengths
(2.414(1) and 2.429(1) Å) are close to their ordinary
value.23 The phosphorus atom is trigonal-pyramidal
with a stereochemically active lone pair. The indenyl
fragments are planar within 0.021 and 0.024 Å, respec-
tively. The angle between the indenyl planes is 70.7°,
Zirconocene 24, involving Cp* and indenyl bearing a
2-Cy2P fragment, was synthesized from Cp*ZrCl3 and
lithium salt of 5 in toluene as shown below (Scheme 16).
This complex was isolated in 67% yield as a yellowish
(22) Inversion at phosphourus is slow, as shown in: (a) Baechler,
R. D.; Mislow, K. J. Am. Chem. Soc. 1970, 92, 3090. (b) Rauk, A.; Allen,
L. C.; Mislow, K. Angew. Chem., Int. Ed. Engl. 1970, 9, 400.
(23) Cambridge Crystallographic Data Base. Cambridge, release
2003.
(24) Ansa-zirconocenes with RP bridges and cationic ansa-complexes
with R2P bridges were described in the following papers.5,7,25

Zr Complexes with 2-R2P-Substituted Indenyl
Organometallics, Vol. 24, No. 12, 2005 3029
Figure 5. PLUTO view of 27. Hydrogen atoms are omitted
Figure 4. Crystal structure of 25. Displacement ellipsoids
are shown at the 50% probability level. Hydrogen atoms
are omitted for clarity. Selected bond lengths (Å) are
Zr(1)-Cl(1) 2.4140(11), Zr(1)-Cl(2) 2.4293(11), Zr(1)-C(1)
2.461(4), Zr(1)-C(2) 2.458(4), Zr(1)-C(3) 2.623(4), Zr(1)-
C(8) 2.623(4), Zr(1)-C(9) 2.496(3), Zr(1)-C(10) 2.458(4),
Zr(1)-C(11) 2.447(4), Zr(1)-C(12) 2.620(4), Zr(1)-C(17)
2.625(3), Zr(1)-C(18) 2.492(4), P(1)-C(1) 1.838(4), P(1)-
C(10) 1.834(4), P(1)-C(19) 1.864(4).
for clarity.
ure 5).27 Since the inversion of phosphorus in this
compound should not occur,22 the interconversion of
meso- and rac-isomers cannot take place. The isolation
of pure rac-isomer seems to be accounted for by lower
solubility of this isomer as compared to the meso-isomer.
It should also be taken into account that the meso-
isomer is less stable due to unfavorable steric repulsion
Scheme 18
t
of Bu groups.
The structure of compound 27 was confirmed by X-ray
diffraction studies. In the structure of 27, chlorine
t
atoms, one of the indenyl ligands, and the bridging -
Bu-P-P-tBu moiety were found to be disordered over
two positions with approximately equal occupancies
(Figure 5). This is related to rotation of the indenyl
ligand as well as chlorine atoms with respect to the
zirconium atom so that the chlorine atoms are rotated
by ca. 20°, while disordered indenyl fragments are
rotated by ca. 7° in the aromatic plane and inclined at
10°. This leads to disordering of the P(tBu)-P(tBu)
fragments. It might be suggested that such disorder is
caused by the sterical effects. In general, the structure
of 27 is typical for ansa-bisindenyl complexes. However,
the low precision of determined parameters prevents the
detailed discussion of its geometry.
and the Cp1-Zr(1)-Cp2 angle is 122.7°. Unlike molecule
22, the five-membered cycles of the indenyl fragments
are disposed in the eclipsed conformation with respect
to each other. The phosphorus atoms are not located in
the indenyl planes (the sums of the bond angles at
carbon atoms C(1) and C(10) are 356.7° and 356.5°,
respectively) due to geometric strain in the ligand (the
bond angle C(1)-P(1)-C(10) is 90.3(2)°). Molecule 25
has the intrinsic symmetry Cs (a mirror plane passes
through the Zr(1), Cl(1), Cl(2), P(1), C(19), and C(21)
atoms), which is not realized in the crystal (space group
P21/c).
Preliminary polymerization results29 show a relatively
low ethylene polymerization activity for 19 and 21/MAO
(Table 1) to give high molecular weight polyethylene,
particularly, in the case of the last catalytic system
Finally, ansa-zirconocene 27 including a P(tBu)P(tBu)
bridge was synthesized from disodium salt of 18 and
ZrCl4(THF)2 in ether and isolated in 52% yield by low-
temperature crystallization from toluene (Scheme 18).
In this case, NaN(TMS)2 instead of nucleophilic lithium
alkyls was used to metalate 18 to exclude possible
nucleophilic cleavage of the P-P bond.26 Interestingly,
the isolated complex is pure rac-isomer with anti
(27) Detailed description of structure of 27 as well as the respective
experimental details will be published elsewhere.
(28) Olefin polymerization in the presence of “open” and ansa-
zirconocenes bearing phosphorus-substituted cyclopentadienyl ligands
was described in: (a) Gobley, O.; Meunier, P.; Gautheron, B.; Gallucci,
J. C.; Erker, G.; Dahlmann, M.; Schloss, J. D.; Paquette, L. A.
Organometallics 1998, 17, 4897. (b) Alt, H. G.; Jung, M. J. Organomet.
Chem. 1998, 568, 127. (c) Schaverien, C. J.; Ernst, R.; Terlouw, W.;
Schut, P.; Sudmeijer, O.; Budzelaar, P. H. M. J. Mol. Catal. A 1998,
128, 245. (d) Shin, J. H.; Hascall, T.; Parkin, G. Organometallics 1999,
18, 6. (e) Antinolo, A.; Fernandez-Galan, R.; Orive, I.; Otero, A.;
Prashar, S. Eur. J. Inorg. Chem. 2002, 2470.
t
configuration of Bu groups, as confirmed by NMR
spectroscopy and X-ray crystal structure analysis (Fig-
(25) (a) Leyser, N.; Schmidt, K.; Brintzinger, H.-H. Organometallics
1998, 17, 2155. (b) Shin, J. H.; Hascall, T.; Parkin, G. Organometallics
1999, 18, 6. (c) Hap, M.; Gilles, T.; Kruck, T.; Tebbe, K.-F. Z.
Naturforsch., B 1999, 54, 482. (d) Shin, J. H.; Bridgewater, B. M.;
Parkin, G. Organometallics 2000, 19, 5155.
(26) Maier, L. In Organic Phosphorous Compounds; Kosolapoff, G.
M., Maier, L., Eds.; Wiley: New York, 1972-1974; Vol. 1, Chapter 2.
(29) (a) MacDowell, D. W. H.; Lindley, W. A. J. Org. Chem. 1982,
47, 705. (b) McEwen, I.; Ro¨nnqvist, M.; Ahlberg, P. J. Am. Chem. Soc.
1993, 115, 3989. (c) Halterman, R. L.; Fahey, D. R.; Bailly, E. F.;
Dockter, D. W.; Stenzel, O.; Shipman, J. L.; Khan, M. A.; Dechert, S.;
Schumann, H. Organometallics 2000, 19, 5464.

3030 Organometallics, Vol. 24, No. 12, 2005
Kazul’kin et al.
Table 1. Ethylene Polymerization (PE) and Ethylene/Octane-1 Copolymerization (PEO) Results for 19, 21,
and 25
run
activity, g/mmol
comonomer
wt %
metallocene
typea
h‚atm
Mw
Mn
PDI
mp, °C
19
21
25
25
PE
600
540
64,050
76,300
532,000
1,374,000
6,130
239,000
484,000
4,260
2.23
2.84
1.44
1.45
PE
PE
130
97
PEOb
6,030
4,160
6.1
a 0.02 µmol of zirconocene, 9.98 µmol of MAO ([Zr]/[Al] ) 1/500), 3.97 mL of toluene, 80 °C, 5 atm of ethylene. b 638 µmol of octene-1.
under vigorous stirring (mechanical stirrer) for 30 min at 0
°C. The resulting mixture was stirred for 10 h at ambient
temperature. Then, the precipitate was filtered off (G3),
washed with 3 × 50 mL of hexanes, and dried in a vacuum.
Yield: 165 g (90%) of a white solid, which was further used
without additional purification.
based on the metallocene bearing 2-diisopropylphosphi-
noindenyl ligands. On the other hand, the catalyst 25/
MAO involving ansa-zirconocene with a PtBu bridge
(Table 1) exhibits very high activity in ethylene polym-
erization and ethylene/octene-1 copolymerization pro-
ducing low molecular weight polymers.
1H-Inden-2-ylphosphonous Dichloride (2). To a suspen-
sion of 4.96 g (10 mmol) of 1 in 50 mL of toluene was added
2.22 mL (2.98 g, 22 mmol) of HSiCl3 at ambient temperature.
This mixture was refluxed for 6 h to form a clear yellow
solution. Volatile components were distilled off at 50 °C, and
the yellow oil formed was dried in a vacuum at this temper-
ature. The crystalline material formed was pure 2. Yield: 2.17
g (99%). Anal. Calcd for C9H7Cl2P: C, 49.81; H, 3.25. Found:
C, 49.67; H, 3.18. 1H NMR (C6D6): δ 7.14-7.17 (m, 4H, 4,5,6,7-
H), 6.92 (dt, J ) 8.1 Hz, J ) 1.7 Hz, 1H, 3-H), 3.61 (d, J ) 1.7
Hz, 2H, 1,1′-H). 13C{1H} NMR (C6D6): δ 147.2 (d, J ) 54.9
Hz), 145.9 (d, J ) 2.8 Hz), 144.1 (d, J ) 54.9 Hz), 142.2 (d, J
) 12.2 Hz), 127.8, 127.0, 124.3, 123.2, 37.9. 31P{1H} NMR
(C6D6): δ 151.4.
1H-Inden-2-yl(diphenyl)phosphine (3). Method A. To
5.18 g (0.026 mol) of 2-bromo-1H-indene and 1.02 g (0.88 mmol)
of Pd(PPh3)4 in 20 mL of toluene were added 4.2 mL (3.05 g,
0.030 mol) of Et3N and then 4.93 g (0.027 mol) of Ph2PH. This
mixture was refluxed for 17 h, cooled to room temperature,
and passed through a short column with silica gel using 350
mL of toluene as eluent. The resulting solution was evaporated
to dryness. The crude product was crystallized from ethanol.
Yield: 6.20 g (76%) of white crystals of 3. Anal. Calcd for
C21H17P: C, 83.98; H, 5.71. Found: C, 83.90; H, 5.63. 1H NMR
(CDCl3): δ 7.30-7.47 (m, 13H, 4,5,7-H in indenyl and PPh2),
7.24 (m, 1H, 6-H in indenyl), 7.15 (dt, J ) 7.3 Hz, J ) 1.2 Hz,
1H, 3-H in indenyl), 3.43 (m, 2H, 1,1′-H in indenyl). 13C{1H}
NMR (CDCl3): δ 146.1 (d, J ) 6.1 Hz), 145.2 (d, J ) 12.2 Hz),
144.6 (d, J ) 7.6 Hz), 140.6 (d, J ) 16.8 Hz), 136.8 (d, J ) 9.2
Hz), 133.6 (d, J ) 19.8 Hz), 128.7 (d, J ) 27.5 Hz), 128.5, 126.5,
125.1, 123.6, 121.0, 42.0 (d, J ) 13.7 Hz). 31P{1H} NMR
(CDCl3): δ 0.3.
Method B. To a mixture of 5.18 g (26.0 mmol) of 2-bromo-
1H-indene and 0.20 g (0.78 mmol) of Pd(MeCN)2Cl2 in 20 mL
of toluene was added 7.23 g (28.0 mmol) of Ph2PSiMe3 at
ambient temperature. This mixture was refluxed for 20 h and
then cooled to ambient temperature and evaporated to dryness
in a vacuum. The residue was recrystallized from hot ethanol.
Yield: 5.07 g (65%) of colorless crystalline product. Anal.
Found: C, 83.72; H, 5.59.
1H-Inden-2-yl(diisopropyl)phosphine (4). Following the
procedure described for the synthesis of 1 (method A) from
Ph2PH, 15.81 g (0.081 mol) of 2-bromo-1H-indene, 9.54 g (0.081
mol) of iPr2PH, 13.9 mL (10.09 g, 0.100 mol) of Et3N, and 2.95
g (2.55 mmol) of Pd(PPh3)4 in 60 mL of toluene gave the title
compound. The crude product was distilled in a vacuum (104-
106 °C/2 mmHg). Yield: 14.8 g (80%) of colorless oil of 4. Anal.
Calcd for C15H21P: C, 77.55; H, 9.11. Found: C, 77.68; H, 9.18.
1H NMR (C6D6): δ 7.35 (m, 1H, 7-H in indenyl), 7.31 (m, 1H,
4-H in indenyl), 7.22 (m, 1H, 5-H in indenyl), 7.17 (m, 1H,
6-H in indenyl), 7.15 (dt, J ) 7.3 Hz, J ) 1.2 Hz, 3-H in
indenyl), 3.35 (m, 2H, 1,1′-H in indenyl), 1.89 (d-sept, J ) 7.0
Hz, J ) 2.3 Hz, 2H, CHMe2), 1.10 (dd, J ) 14.7 Hz, J ) 7.0
Hz, 6H, CHMe2), 0.97 (dd, J ) 11.7 Hz, J ) 7.0 Hz, 6H,
In conclusion, we elaborated straightforward meth-
ods, including Pd-catalyzed pathways, to synthesize
dialkyl/aryl/inden-2-yl- and alkyl/aryl/diinden-2-ylphos-
phines, as well as 1,2-di-tert-butyl-1,2-di(1H-inden-2-yl)-
diphosphane, of importance for developing new families
of olefin polymerization catalysts. Preliminary studies
showed that the zirconocenes obtained are active cata-
lysts of ethylene polymerization and ethylene/octane-1
copolymerization.
Experimental Section
All manipulations were performed either in an atmosphere
of thoroughly purified argon using the standard Schlenk
technique or in a controlled atmosphere glovebox (VAC).
Tetrahydrofuran and ether for synthesis were purified by
distillation over LiAlH4 and kept over sodium benzophenone
ketyl or Na/K alloy. Hydrocarbon solvents (including benzene-
d6 for NMR measurements) were distilled and stored over
CaH2 or Na/K alloy. Methylene chloride-d2 was distilled and
stored over CaH2. Chloroform-d was distilled over P4O10 and
stored over molecular sheves (3 Å). Iodobenzene (Acros),
indene, tech. (Acros), Ph2PH (Strem), PhPH2 (Strem), Cy2PH
(Strem), triethyl phosphite (Acros), LiAlH4 (Aldrich), CuCN
(Merck), PCl5 (Merck), HSiCl3 (Aldrich), triethylamine (Acros),
NaN(TMS)2 (Aldrich), nBuLi in hexanes (Chemetall), MeLi in
ether (Aldrich), tBuLi in pentane (Acros), and tBuMgCl in ether
(Aldrich) were used as obtained. Triethylamine (Acros) was
dried with CaH2, then was distilled from sodium. 2-Bromo-
1H-indene,29 1H-inden-2-yl trifluoromethanesulfonate,30 PdCl2-
(MeCN)2,31 Pd(PPh3)4,32 ZrCl4(THF)2,33 iPr2PH,34 tBu2PH,34
tBuPH2,35 and Ph2PSiMe3 were prepared according to the
36
published methods. Celite 403 (Fluka) was dried in a vacuum
for 20 h at 200 °C. 1H, 13C, and 31P spectra were recorded with
Varian VXR-400 or Bruker DPX-300 spectrometers for 1-10%
1
solutions in deuterated solvents. Chemical shifts for H and
1
13C were measured relative to TMS. In H NMR spectra, the
assignment was made on the evidence of double resonance and
NOE experiments. Chemical shifts for 31P were measured
relative to H3PO4. C, H microanalyses were done using a CHN-
O-Rapid analyzer (Heracus).
Trichloro(1H-inden-2-yl)phosphonium Hexachloro-
phosphate(1-) (1). To a suspension of 154 g (0.74 mol) of
PCl5 in 200 mL of toluene was added a solution of 48.2 mL
(43.0 g, 0.37 mol) of indene (tech., 90%) in 30 mL of toluene
(30) Radivoy, G.; Yus, M.; Alonso, F. Tetrahedron 1999, 55, 14479.
(31) Hartley, F. R.; Murray, S. G.; McAuliffe, C. A. Inorg. Chem.
1979, 18, 1394.
(32) Coulson, D. R. Inorg. Synth. 1972, 13, 121.
(33) Manzer, L. E. Inorg. Synth. 1982, 22, 135.
(34) Hoff, M. C.; Hill, P. J. Org. Chem. 1959, 24, 56.
(35) Becker, G.; Rossler, O.; Schneider, E. Z. Anorg. Allg. Chem.
1978, 443, 42.
(36) Tunney, S. E.; Stille, J. K. J. Org. Chem. 1987, 52, 748.

Zr Complexes with 2-R2P-Substituted Indenyl
Organometallics, Vol. 24, No. 12, 2005 3031
CHMe2*). 13C{1H} NMR (C6D6): δ 146.1 (d, J ) 3.1 Hz), 145.0
(d, J ) 10.7 Hz), 144.7 (d, J ) 24.4 Hz), 142.4 (d, J ) 25.9
Hz), 126.7, 125.2, 123.8, 121.2, 42.8 (d, J ) 4.6 Hz), 23.8 (d, J
) 12.2 Hz), 20.4 (d, J ) 18.3 Hz), 20.0 (d, J ) 10.7 Hz). 31P-
{1H} NMR (C6D6): δ 14.9.
4-H), 7.21 (m, 1H, 5-H), 7.10 (m, 1H, 6-H), 6.86 (m, 1H, 3-H),
3.41 (m, 2H, 1,1′-H in indenyl), 1.24 (d, 6H, J ) 2.3 Hz, Me).
13C{1H} NMR (CDCl3): δ 150.7 (d, J ) 15.3 Hz), 145.0 (d, J )
4.6 Hz), 144.8 (d, J ) 6.1 Hz), 134.5 (d, J ) 14.3 Hz), 126.2,
124.3, 123.3, 120.2, 40.3 (d, J ) 12.2 Hz), 29.5, 13.4 (d, J )
12.2 Hz). 31P{1H} NMR (CDN˜ l3): δ -56.0.
Method B. To a solution of 2.17 g (10 mmol) of 2 in 60 mL
of diethyl ether-hexanes (1:1, vol) was added dropwise 10.9
mL of 1.84 M MeLi (20 mmol) in ether under vigorous stirring
for 2 h at -90 °C. The reaction mixture was slowly warmed to
ambient temperature, stirred overnight, and then filtered
though a glass frit (G4). The precipitate was additionally
washed with 10 mL of ether. The combined extract was
evaporated to dryness, and the residue was dried in a vacuum.
Yield: 1.76 g (99%) of colorless crystalline solid. Anal. Found:
C, 75.19; H, 7.50.
Dicyclohexyl(1H-inden-2-yl)phosphine (5). Method A.
Following the procedure described for the synthesis of 1
(method A) from Ph2PH, 13.02 g (0.067 mol) of 2-bromo-1H-
indene, 12.84 g (0.065 mol) of Cy2PH, 10.3 mL (7.48 g, 0.074
mol) of Et3N, and 1.55 g (1.34 mmol) of Pd(PPh3)4 in 50 mL of
toluene gave the title compound. The crude product was
crystallized from ethanol. Yield: 15.33 g (76%) of yellowish
crystals of 5. Anal. Calcd for C21H29P: C, 80.73; H, 9.36.
Found: C, 80.41; H, 9.45. 1H NMR (C6D6): δ 7.33 (m, 1H, 7-H
in indenyl), 7.28 (m, 1H, 4-H in indenyl), 7.15-7.23 (m, 2H,
5,6-H in indenyl), 7.12 (dt, J ) 7.3 Hz, J ) 1.2 Hz, 1H, 3-H in
indenyl), 3.38 (m, 2H, 1,1′-H in indenyl), 1.02-1.98 (m, 20H,
PCy2). 13C{1H} NMR (C6D6): δ 146.2, 145.2 (d, J ) 10.7 Hz),
144.7 (d, J ) 24.4 Hz), 142.8 (d, J ) 29.0 Hz), 126.8, 125.2,
123.8, 121.2, 42.9 (d, J ) 3.1 Hz), 33.8 (d, J ) 11.8 Hz), 30.9
(d, J ) 15.3 Hz), 30.4 (d, J ) 9.2 Hz), 27.5 (d, J ) 12.0 Hz),
27.4 (d, J ) 7.6 Hz). 31P{1H} NMR (C6D6): δ 5.7.
Method B. Compound 5 was prepared also via Pd-catalyzed
phosphination of 1H-inden-2-yl trifluoromethanesulfonate.
Following the procedure described for the synthesis of 3 from
Ph2PH, 6.60 g (0.025 mol) of 1H-inden-2-yl trifluoromethane-
sulfonate, 4.98 g (0.025 mol) of Cy2PH, 3.9 mL (2.82 g, 0.027
mol) of Et3N, and 0.72 g (0.62 mmol) of Pd(PPh3)4 in 50 mL of
toluene gave the title compound. Yield: 7.81 g (82%) of 5. Anal.
Found: C, 80.63; H, 9.31.
tert-Butyl(1H-inden-2-yl)phosphinous Chloride (8). To
a solution of 1.09 g (5.0 mmol) of 2 in 40 mL of diethyl ether-
hexanes (1:1, vol) was added dropwise 4.7 mL of 1.06 M
tBuMgCl in ether under vigorous stirring for 2 h at -90 °C.
The resulting mixture was slowly warmed to ambient tem-
perature, stirred overnight, and filtered through a glass frit
(G3). The precipitate was additionally washed with 3 × 15 mL
of ether. The combined filtrate was evaporated to dryness, and
the residue was dried in a vacuum. Yield: 1.19 g (99%) of
colorless solid. Anal. Calcd for C13H16ClP: C, 65.41; H, 6.76.
1
Found: C, 65.62; H, 7.85. H NMR (C6D6): δ 7.15-7.34 (m,
5H, 3,4,5,6,7-H), 3.43-3.68 (m, 1,1′-H in indenyl), 1.11 (d, J
t
) 14.0 Hz, 9H, Bu). 13C{1H} NMR (C6D6): δ 146.1, 144.5 (d,
J ) 45.8 Hz), 144.1 (d, J ) 10.7 Hz), 142.9 (d, J ) 35.1 Hz),
126.9, 126.2, 124.0, 121.9, 42.6 (d, J ) 6.1 Hz), 34.8 (d, J )
29.0 Hz), 25.8 (d, J ) 18.3 Hz). 31P{1H} NMR (C6D6): δ 104.5.
Di(tert-butyl)(1H-inden-2-yl)phosphine (6). To 40 mL
Diethyl 1H-Inden-2-ylphosphonate (9). To 91.0 g (0.467
mol) of 2-bromo-1H-indene and 3.02 g (0.023 mol) of NiCl2 in
a 250 mL flask equipped with a distillation head was added
85.0 mL (82.4 g, 0.496 mol) of (EtO)3P. This black mixture was
heated in an oil bath at 185-190 °C for 3 h. During this
procedure, argon gas was bubbled through the mixture to
eliminate ethyl bromide formed (actually, its mixture with the
starting triethyl phosphite). The crude product was distilled
in a vacuum (171-175 °C/1 mmHg). Yield: 102.4 g (87%) of a
colorless oil of 9. Anal. Calcd for C13H17O3P: C, 61.90; H, 6.79.
t
of THF were added 12.4 mL of 1.70 M BuLi (21 mmol) in
pentane and then 1.88 g (21 mmol) of CuCN. The resulting
mixture was warmed under vigorous stirring for 30 min to -70
°C. Then, 5.00 g (21 mmol) of 8 in 40 mL of THF was added in
one portion. The mixture was slowly (ca. 5 h) warmed to
ambient temperature, stirred for 24 h, and then evaporated
to dryness. The product was extracted with 3 × 50 mL of
toluene. The combined toluene extract was filtered through a
glass frit (G4) and evaporated to dryness. High-vacuum
sublimation (0.01 mmHg, 150-190 °C) gave 1.49 g (27%) of 6.
Anal. Calcd for C17H25P: C, 78.42; H, 9.68. Found: C, 78.23;
H, 9.56. 1H NMR (C6D6): δ 7.44 (m, 1H, 7-H), 7.39 (m, 1H,
4-H), 7.22-7.35 (m, 2H, 5,6-H), 6.12 (dt, J ) 7.3 Hz, J ) 1.5
Hz, 1H, 3-H), 3.66 (m, 2H, 1,1′-H in indenyl), 1.27 (d, J ) 1.5
1
Found: C, 62.03; H, 6.82. H NMR (CDN˜ l3): δ 7.63 (m, 1H,
3-H), 7.51 (m, 2H, 4,7-H), 7.32 (m, 2H, 5,6-H), 4.07-4.23 (m,
4H, OCH2Me), 3.65 (m, 2H 1,1′-H in indenyl), 1.35 (t, J ) 7.0
Hz, 6H, Me). 31P{1H} NMR (CDN˜ l3): δ 31.2.
1H-Inden-2-yl(dimethyl)phosphine Oxide (13). To a
solution of 12.6 g (50 mmol) of 9 in 100 mL of diethyl ether
was added dropwise 81.5 mL of 1.84 M MeLi (150 mmol) in
ether under vigorous stirring for 2 h at -30 °C. The resulting
mixture was stirred overnight at ambient temperature; then,
20 mL of 10% HCl was added. The resulting mixture was
additionally stirred for 1 h. The ether layer was separated,
dried over anhydrous Na2SO4, and evaporated to dryness. The
yellow-brown oil obtained was recrystallized from chloroform.
Yield: 3.70 g (30%) of the title compound as a mono solvate
with H2O and HCl. Anal. Calcd for C11H13OP: C, 68.74; H,
6.82. Found: C, 68.98; H, 6.90. 1H NMR (CDN˜ l3): δ 7.44-
7.53 (m, 3H, 3,5,7-H), 7.24-7.36 (m, 2H, 4,6-H), 3.63 (m, 2H,
1,1′-H in indenyl), 2.30 (br s, 3H, H2O and HCl), 1.70 (d, J )
13.0 Hz, 6H, Me). 13C{1H} NMR: δ 145.0 (d, J ) 7.6 Hz), 142.9
(d, J ) 16.8 Hz), 141.9 (d, J ) 10.7 Hz), 140.6 (d, J ) 103.8
Hz), 127.0, 126.9, 124.0, 122.6, 30.5 (d, J ) 12.2 Hz), 17.7 (d,
J ) 73.2 Hz). 31P{1H} NMR (CDN˜ l3): δ 44.5.
t
Hz, 18H, Bu). 13C{1H} NMR (C6D6): δ 146.3 (d, J ) 2.3 Hz),
145.5 (d, J ) 32.9 Hz), 144.5 (d, J ) 12.0 Hz), 127.0 (d, J )
7.5 Hz), 126.7, 125.6, 123.7, 121.4, 44.7 (d, J ) 3.8 Hz), 32.5
(d, J ) 18.7 Hz), 27.5 (d, J ) 14.2 Hz). 31P{1H} NMR (C6D6):
δ 22.8 (br s).
1H-Inden-2-ylphosphine (10) and Compound 12. To a
suspension of 13.3 g (0.350 mol) of LiAlH4 in 200 mL of ether
was added dropwise over 2 h a solution of 58.7 g (0.233 mol)
of 9 in 140 mL of ether. The resulting mixture was refluxed
for 2 h and then cooled to room temperature, and 50 mL of
water was added dropwise to decompose an excess of metal
hydrides. The ether solution was separated, and the residue
was diluted with 2 × 200 mL of ether. The combined extract
was evaporated to ca. 100 mL. A white solid that precipitated
at -30 °C was separated, washed with 10 mL of cold ether,
and dried in a vacuum. Yield: 2.39 g (7%) of compound 12.
The yellow solution was evaporated, and the obtained oil was
distilled in a vacuum (108-110 °C/8 mmHg). Yield: 21.90 g
of a ca. 4 to 1 mixture of 10 (51%) and 11 (12%). Additional
careful fractional distillation of this mixture gave 14.52 g of
10 of 93% purity (31P NMR). Compound 10. Anal. Calcd for
1H-Inden-2-yl(dimethyl)phosphine (7). Method A. To
a solution of 3.40 g (13.8 mmol) of 13‚H2O‚HCl in 100 mL of
CH2Cl2 was added at 0 °C 5.61 g (4.18 mL, 41.4 mmol) of
HSiCl3. The reaction mixture was stirred for 24 h at room
temperature and then evaporated to dryness. The crude
product was purified by flash chromatography on silica gel 60
(d 30 mm, l 50 mm; eluent: benzene). Yield: 2.33 g (96%).
Anal. Calcd for C11H13P: C, 74.98; H, 7.44. Found: C, 75.22;
1
C9H9P: C, 72.97; H, 6.12. Found: C, 72.85; H, 6.20. H NMR
(C6D6): δ 7.15-7.27 (m, 3H, 5,6,7-H), 7.06-7.12 (m, 1H, 3-H),
6.83-6.87 (m, 1H, 4-H), 3.56 (m, JP-H ) 199.6 Hz, 2H, PH2),
1
H, 7.51. H NMR (CDCl3): δ 7.38 (m, 1H, 7-H), 7.29 (m, 1H,

3032 Organometallics, Vol. 24, No. 12, 2005
Kazul’kin et al.
3.05 (m, 2H, 1,1′-H). 13C NMR (C6D6): δ 146.2, 145.3 (d, J )
9.2 Hz), 142.0 (d, J ) 26.0 Hz), 134.8 (d, J ) 13.7 Hz), 126.6,
125.2, 123.5, 120.8, 46.7. 31P NMR (C6D6): δ -131.6 (dt, JP-H
) 199.6 Hz, JP-H ) 7.8 Hz). Compound 11. 31P NMR (C6D6):
δ -102.6 (m, JP-H) 189.5 Hz, JP-H ) 11.7 Hz, JP-H ) 9.8 Hz).
Compound 12. Anal. Calcd for C27H23P3: C, 73.64; H, 5.26.
was refluxed for 13 h, cooled to room temperature, and passed
through a short column with silica gel using 150 mL of toluene
as eluent. The resulting solution was evaporated to dryness.
The crude product was crystallized from ethanol. Yield: 1.63
g (28%) of white crystals of 16. Anal. Calcd for C24H19P: C,
85.19; H, 5.66. Found: C, 85.01; H, 5.58. 1H NMR (CDN˜ l3): δ
7.53 (m, 4H, 2,6-H in C6H5), 7.38 (m, 2H, 7-H in indenyl), 7.35
(m, 6H, 3,4,5-H in C6H5), 7.33 (m, 2H, 4-H in indenyl), 7.16
(m, 2H, 5-H in indenyl), 7.24 (m, 2H, 6-H in indenyl), 7.01 (m,
2IÄ, 3-H in indenyl), 3.47 (m, 4IÄ, 1,1′-H in indenyl). 13C{1H}
NMR (CDCl3): δ 145.9 (d, J ) 3.1 Hz), 144.6 (d, J ) 7.6 Hz),
140.3 (d, J ) 18.3 Hz), 136.5 (d, J ) 4.6 Hz), 133.7, (d, J )
19.8 Hz), 129.1, 128.9 (d, J ) 6.1 Hz), 126.6 (d, J ) 6.1 Hz),
126.5, 125.1, 123.6, 121.0, 42.1 (a¨, J ) 13.7 Hz). 31P{1H} NMR
(C6D6): δ -29.7.
1
Found: C, 73.56; H, 5.20. For H NMR spectrum (in CD2Cl2)
see the Supporting Information. 31P{1H} NMR (CD2N˜ l2): δ 36.2
(d, JP-P ) 270.9 Hz), -26.0 (dd, JP-P ) 235.9 Hz, JP-P ) 270.9
Hz), -40.3 (d, JP-P ) 235.9 Hz). 31P NMR (CD2N˜ l2): δ 36.2 (d,
JP-P ) 270.9 Hz), -26.0 (ddd, JP-P ) 270.9 Hz, JP-P ) 235.9
Hz, JP-H ) 16.9 Hz), -40.3 (dddt, JP-P ) 235.9 Hz, JP-H
208.9 Hz, JP-H ) 19.0 Hz, JP-H ) 12.4 Hz).
)
tert-Butyl(1H-inden-2-yl)phosphine (14). To 9.61 g (0.049
mol) of 2-bromo-1H-indene and 1.13 g (0.98 mmol) of Pd(PPh3)4
in 25 mL of toluene were added 7.5 mL (5.45 g, 0.054 mol) of
A Mixture of d-/l- and meso-1,2-Di-tert-butyl-1,2-di(1H-
inden-2-yl)diphosphanes (18). To a solution of 335 mg (1.74
mmol) of 14 in 3 mL of diethyl ether were added 0.49 mL (356
mg, 3.52 mmol) of triethylamine and 415 mg (1.74 mmol) of 8
at -78 °C. The reaction mixture was slowly warmed to
ambient temperature under vigorous stirring. This mixture
was additionally stirred for 5 h at room temperature and 100
h at 40 °C and then evaporated to dryness. The residue was
dissolved in 50 mL of toluene. This solution in a glovebox was
passed through a short column with silica gel 60 (d 20 mm, l
70 mm). This column was additionally washed with 250 mL
of toluene. The combined extract was evaporated to dryness
to give a white solid. Yield: 357 mg (51%) as a mixture of d-/
l-(trans-) and meso-(cis-)isomers in a ratio ca. 3 to 2. Anal.
Calcd for C26H32P2: C, 76.83; H, 7.93. Found: C, 76.99; H, 8.01.
t
Et3N and 4.88 g (0.054 mol) of BuPH2. This mixture was
refluxed for 14 h, cooled to room temperature, and filtered
through a glass frit (G3) to separate from the compound 15.
The filtrate was evaporated to dryness. The crude product was
distilled in a vacuum (108-110 °C/3 mmHg). Yield: 3.07 g
(31%) of crystalline solid of 14. Anal. Calcd for C13H17P: C,
76.45; H, 8.39. Found: C, 76.32; H, 8.33. 1H NMR (CDCl3): δ
7.42 (m, 1H, 7-H), 7.36 (m, 1H, 4-H), 7.25 (m, 1H, 5-H), 7.16
(m, 1H, 6-H), 7.06 (m, 1H, 3-H), 3.86 (br s, 1H, PH), 3.56 (m,
2H, 1,1′-H in indenyl), 1.18 (d, 9H, J ) 12.9 Hz, tBu). 13C{1H}
NMR (CDCl3): δ 145.9 (d, J ) 3.3 Hz), 145.1 (d, J ) 6.1 Hz),
141.4 (d, J ) 19.8 Hz), 140.7 (d, J ) 16.8 Hz), 126.4, 124.8,
123.3, 120.6, 45.8 (d, J ) 7.6 Hz), 30.2 (d, J ) 13.7 Hz), 29.4
(d, J ) 7.6 Hz). 31P{1H} NMR (CDCl3): δ -28.7 (d, J ) 207.4
Hz).
1
d-/l-18. H NMR (C6D6): δ 7.27 (m, 2H, 3-H in indenyl), 7.19
(m, 2H, 7-H in indenyl), 7.09 (m, 2H, 5-H in indenyl), 6.89 (m,
2H, 6-H in indenyl), 6.76 (m, 2H, 4-H in indenyl), 3.12 (d, J )
22.6 Hz, 2H, 1-H in indenyl), 2.65 (d, J ) 22.6 Hz, 2H, 1′-H in
tert-Butyl[di(1H-inden-2-yl)]phosphine (15). To 15.61
g (0.080 mol) of 2-bromo-1H-indene and 1.38 g (1.19 mmol) of
Pd(PPh3)4 in 60 mL of toluene were added 22.3 mL (16.19 g,
t
indenyl), 1.27 (t, J ) 6.9 Hz, 18H, Bu). 13C NMR (C6D6): δ
t
0.160 mol) of Et3N and 3.60 g (0.040 mol) of BuPH2. This
148.8, 146.6, 144.7 (t, J ) 18.7 Hz), 144.3, 126.5, 125.4, 123.6,
121.2, 43.4, 29.8 (t, J ) 11.5 Hz), 25.7. 31P{1H} NMR (C6D6):
δ -13.1. meso-18. 1H NMR (C6D6): δ 7.48 (m, 2H, 3-H in
indenyl), 7.24 (m, 2H, 7-H in indenyl), 7.07 (m, 2H, 5-H in
indenyl), 7.04 (m, 2H, 6-H in indenyl), 7.01 (m, 2H, 4-H in
indenyl), 3.80 (d, J ) 22.9 Hz, 2H, 1-H in indenyl), 3.55 (d, J
) 22.9 Hz, 2H, 1′-H in indenyl), 0.97 (t, J ) 6.4 Hz, 18H, tBu).
13C{1H} NMR (C6D6): δ 148.5, 146.7, 145.5 (t, J ) 18.4 Hz),
144.0, 126.8, 125.8, 124.0, 121.5, 44.3, 30.1 (t, J ) 9.3 Hz),
26.0. 31P{1H} NMR (C6D6): δ -19.5.
Complex 19. To a solution of 5.12 g (17.0 mmol) of 3 in
100 mL of ether was added 9.3 mL (17.0 mmol) of 1.83 M MeLi
in ether at -90 °C. This mixture was stirred for 4 h at ambient
temperature; then, 3.13 g (8.3 mmol) of ZrCl4(THF)2 was added
at -90 °C. The mixture was stirred for 24 h at room temper-
ature and then filtered through glass frit (G4). The precipitate
was washed with 300 mL of hot toluene. To this toluene extract
was added 300 mL of hexanes. The precipitate formed was
separated by filtration (G3), washed with 3 × 20 mL of
hexanes, and dried in a vacuum. Yield: 3.75 g (58%) of a yellow
crystalline solid of 19. Anal. Calcd for C42H32Cl2P2Zr: C, 66.31;
H, 4.24. Found: C, 66.17; H, 4.18. 1H NMR (CD2Cl2): δ 7.43-
7.48 (dd, J ) 6.4 Hz, J ) 3.1 Hz, 4H, 5,6-H in indenyl), 7.26-
7.37 (m, 20H, C6H5), 7.07-7.13 (dd, J ) 6.4 Hz, J ) 3.1 Hz,
4H, 4,7-H in indenyl), 6.21 (s, 4H, 1,3-H in indenyl). 13C{1H}
NMR (CD2Cl2): δ 138.6 (d, J ) 4.6 Hz), 138.5 (d, J ) 4.6 Hz),
136.1 (d, J ) 7.7 Hz), 136.0 (d, J ) 10.7 Hz), 135.9 (d, J )
10.7 Hz), 135.8 (d, J ) 7.7 Hz), 130.9, 130.1 (d, J ) 3.0 Hz),
130.0 (d, J ) 3.0 Hz), 129.8 (d, J ) 1.5 Hz), 127.9, 126.4, 112.3
(d, J ) 6.1 Hz), 112.2 (d, J ) 6.1 Hz). 31P{1H} NMR (CD2Cl2):
δ -16.4.
mixture was refluxed for 24 h, cooled to room temperature,
and passed through a short column with silica gel using 200
mL of toluene as eluent. The filtrate was evaporated to dryness
to give an oil, which after treatment with 150 mL of hot
ethanol gave a gray precipitate. This precipitate was separated
(G3), washed with 3 × 5 mL of cold ethanol, and dried in a
vacuum. Yield: 10.83 g (85%) of 15. Anal. Calcd for C22H23P:
1
C, 82.99; H, 7.28. Found: C, 82.71; H, 7.38. H NMR (C6D6):
δ 7.26 (m, 2H, 7-H), 7.23 (m, 2H, 5-H), 7.13-7.19 (m, 4H, 3,6-
H), 7.11 (m, 2H, 4-H), 3.42 (s, 4IÄ, 1,1′-H in indenyl), 1.14 (d, J
) 12.6 Hz, 9H, tBu). 13C{1H} NMR (C6D6): δ 148.0 (d, J ) 4.6
Hz), 144.9 (d, J ) 9.2 Hz), 144.6 (d, J ) 22.9 Hz), 141.8 (d, J
) 24.4 Hz), 126.8, 125.3, 123.8, 121.2, 43.9 (d, J ) 9.2 Hz),
31.0 (d, J ) 12.2 Hz), 29.0 (d, J ) 13.7 Hz). 31P{1H} NMR
(C6D6): δ -6.4.
1H-Inden-2-yl(phenyl)phosphine (17). To 7.40 g (0.050
mol) of 10 and 2.88 g (2.49 mmol) of Pd(PPh3)4 in 20 mL of
toluene were added 7.7 mL (5.59 g, 0.055 mol) of Et3N and
then 5.6 mL (10.21 g, 0.050 mol) of iodobenzene. This mixture
was refluxed for 8 h, cooled to room temperature, and passed
through a short column with silica gel using 30 mL of toluene
as eluent. The resulting solution was evaporated to dryness.
The crude product was distilled in a vacuum (120-121 °C/2
mm). Yield: 5.71 g (51%) of a colorless oil of 17. Anal. Calcd
1
for C15H13P: C, 80.34; H, 5.84. Found: C, 80.22; H, 5.90. H
NMR (C6D6): δ 7.08-7.68 (m, 10H, 3,4,5,6,7-H in indenyl and
C6H5), 5.13 (d, J ) 216.3 Hz, 1H, PH), 3.24 (m, 2H, 1,1′-H in
indenyl). 13C{1H} NMR (C6D6): δ 146.4 (d, J ) 3.1 Hz), 145.2
(d, J ) 9.2 Hz), 141.7 (d, J ) 15.3 Hz), 141.4 (d, J ) 24.4 Hz),
134.0 (d, J ) 16.8 Hz), 128.8 (d, J ) 6.1 Hz), 128.6 (d, J ) 6.1
Hz), 128.5, 126.7, 125.4, 123.8, 121.2, 43.7 (d, J ) 4.6 Hz). 31P-
{1H} NMR (C6D6): δ -43.1 (d, J ) 211.3 Hz).
Di(1H-inden-2-yl)(phenyl)phosphine (16). To 4.00 g
(0.021 mol) of 2-bromo-1H-indene and 0.46 g (0.40 mmol) of
Pd(PPh3)4 in 20 mL of toluene were added 3.2 mL (2.32 g, 0.023
mol) of Et3N and then 4.52 g (0.020 mol) of 17. This mixture
Complex 20. To a solution of 7.05 g (40 mmol) of 7 in 100
mL of diethyl ether was added dropwise 21.8 mL of 1.84 M
(40 mmol) MeLi in ether under vigorous stirring at -90 °C.
The reaction mixture was slowly warmed to ambient temper-
ature and stirred for 4 h. To this solution cooled to -90 °C

Zr Complexes with 2-R2P-Substituted Indenyl
Organometallics, Vol. 24, No. 12, 2005 3033
was added 7.55 g (20 mmol) of ZrCl4(THF)2. The resulting
mixture was stirred for 12 h at ambient temperature and
evaporated to dryness, and 50 mL of toluene was added. This
suspension was stirred for 12 h and then filtered through a
glass frit (G4). The precipitate was additionally washed by 3
× 100 mL of hot toluene. The combined extracts were
evaporated to ca. 100 mL, and 150 mL of hexanes was added.
Crystals that precipitated from this solution at -30 °C were
collected, washed with 20 mL of cold toluene and 3 × 20 mL
of hexanes, and dried in a vacuum. Yield: 12.5 g (61%). Anal.
Calcd for C22H24Cl2P2Zr: C, 51.56; H, 4.72. Found: C, 51.42;
C34H48Cl2P2Zr: C, 59.98; H, 7.11. Found: C, 60.19; H, 7.20.
1H NMR (C6D6): δ 7.53-7.59 (dd, J ) 6.5 Hz, J ) 3.0 Hz, 4H,
5,6-H in indenyl), 7.135 (s, 2H, 1/3-H in indenyl), 7.130 (s, 2H,
3/1-H in indenyl), 7.06-7.11 (dd, J ) 6.5 Hz, J ) 3.0 Hz, 4H,
4,7-H in indenyl), 1.30 (d, J ) 11.2 Hz, 36H, tBu). 31P{1H} NMR
(C6D6): δ 34.6.
Complex 24. To a solution of 1.50 g (4.80 mmol) of 5 in 35
mL of toluene was added 1.92 mL of 2.5 M (4.80 mmol) of
nBuLi in hexanes at ambient temperature. This mixture was
stirred for 12 h at this temperature; then, 1.60 g (4.80 mmol)
of Cp*ZrCl3 was added. The resulting mixture was stirred for
12 h at ambient temperature and 12 h at 90 °C and then
filtered through Celite 403. The filtrate was evaporated to ca.
20 mL. Crystals precipitated at -30 °C were collected, washed
with 3 × 20 mL of hexanes, and dried in a vacuum. Yield: 2.01
g (67%). Anal. Calcd for C31H43Cl2PZr: C, 61.16; H, 7.12.
Found: C, 60.92; H, 7.04. 1H NMR (CD2Cl2): δ 7.58-7.64 (dd,
J ) 6.5 Hz, J ) 3.0 Hz, 2H, 5,6-H in indenyl), 7.28-7.34 (dd,
J ) 6.5 Hz, J ) 3.0 Hz, 2H, 4,7-H in indenyl), 6.79 (s, 2H,
1,3-H in indenyl), 2.21 (s, 15H, C5Me5), 2.29-2.41, 1.84-2.08,
and 1.33-1.67 (m, 22H, N˜ o´). 13C{1H} NMR (CD2Cl2): δ 135.7,
129.5, 126.3, 125.2, 124.3, 109.0 (d, J ) 9.2 Hz), 34.4 (d, J )
15.3 Hz), 34.7 (d, J ) 18.3 Hz), 31.5 (d, J ) 9.2 Hz), 28.2 (d, J
) 12.2 Hz), 28.0 (d, J ) 9.2 Hz), 27.0, 13.2. 31P{1H} NMR (CD2-
Cl2): δ -8.9.
1
H, 4.64. H NMR (CD2Cl2): δ 7.45-7.51 (dd, J ) 6.4 Hz, J )
3.1 Hz, 4H, 5,6-H), 7.12-7.18 (dd, J ) 6.4 Hz, J ) 3.1 Hz, 4H,
4,7-H), 6.44 (s, 4H, 1,3-H in indenyl), 1.25 (d, J ) 1.8 Hz, 6H,
Me), 1.24 (d, J ) 1.8 Hz, 6H, Me*). 13C{1H} NMR (CD2Cl2): δ
130.5, 130.0, 127.6, 126.3, 110.4 (d, J ) 6.1 Hz), 110.3 (d, J )
6.1 Hz), 16.1 (d, J ) 3.8 Hz), 16.0 (d, J ) 3.8 Hz). 31P{1H}
NMR (CD2Cl2): δ -48.8.
Complex 21. To a solution of 5.02 g (21.6 mmol) of 4 in 70
mL of ether was added 10.8 mL (21.6 mmol) of 2.00 M MeLi
in ether at -90 °C. This mixture was stirred for 4 h at ambient
temperature; then, 4.02 g (10.6 mmol) of ZrCl4(THF)2 was
added at -90 °C. This mixture was stirred for 18 h at room
temperature and then evaporated to dryness. The residue was
washed with 100 mL of ether. The resulting yellow solution
was filtered (G4) and evaporated to ca. 2/3 of its initial volume.
Crystallization of this solution at -30 °C gave orange crystals
of 21, which were separated, washed with 5 mL of cold ether,
and dried in a vacuum. Yield: 2.91 g (43%). Anal. Calcd for
C30H40Cl2P2Zr: C, 57.68; H, 6.45. Found: C, 57.83; H, 6.52.
1H NMR (CD2Cl2): δ 7.46-7.52 (dd, J ) 6.4 Hz, J ) 3.1 Hz,
4H, 5,6-H), 7.13-7.19 (dd, J ) 6.4 Hz, J ) 3.1 Hz, 4H, 4,7 H),
6.46 (s, 4H, 1,3-H in indenyl), 2.05 (d-sept, 4H, J ) 6.9 Hz, J
) 1.5 Hz, CHMe2), 1.18 (dd, J ) 13.4 Hz, J ) 7.0 Hz, 12H,
CHMe2), 0.98 (dd, J ) 12.8 Hz, J ) 6.9 Hz, 12H, CHMe2*).
13C{1H} NMR (CD2Cl2): δ 135.5, 135.2, 129.9, 128.0, 126.4,
112.2 (d, J ) 7.6 Hz), 112.1 (d, J ) 7.6 Hz), 25.9, 25.7, 21.9 (d,
J ) 13.6 Hz), 21.5 (d, J ) 15.3 Hz). 31P{1H} NMR (CD2Cl2): δ
4.6.
Complex 25. To a solution of 4.66 g (14.6 mmol) of 15 in
130 mL of ether was added 16.0 mL (29.2 mmol) of 1.83 M
MeLi in ether at -90 °C. This mixture was stirred for 3 h at
ambient temperature, and then, 5.37 g (14.2 mmol) of ZrCl4-
(THF)2 was added at -90 °C. The mixture was stirred for 48
h at room temperature and then filtered through glass frit
(G4). The precipitate was washed with 5 × 100 mL of hot
toluene. The combined extract was evaporated to 2/3 of its
initial volume. Crystallization of the solution at -30 °C gave
yellow crystals of 25. Yield: 3.81 g (56%). Anal. Calcd for
C22H21Cl2PZr: C, 55.22; H, 4.42. Found: C, 55.47; H, 4.49. 1H
NMR (CD2Cl2): δ 7.57 (dq, J ) 8.5 Hz, J ) 1.0 Hz, 2H, 4/7-IÄ
in indenyl), 7.42 (dq, J ) 8.5 Hz, J ) 1.0 Hz, 2H, 7/4-IÄ in
indenyl), 7.24 (ddd, J ) 8.5 Hz, J ) 6.5 Hz, J ) 1.2 Hz, 2IÄ,
5/6-H in indenyl), 7.17 (ddd, J ) 8.5 Hz, J ) 6.5 Hz, J ) 1.2
Hz, 2IÄ, 5/6-H in indenyl), 6.62 (dt, J ) 2.6 Hz, J ) 1.0 Hz, 2IÄ,
1/3-H in indenyl), 6.36 (ddd, J ) 5.6 Hz, J ) 2.6 Hz, J ) 1.0
Complex 22. To a solution of 4.14 g (13.0 mmol) of 5 in 70
mL of ether was added 5.3 mL (13.0 mmol) of 2.50 M nBuLi in
hexanes at -90 °C. This mixture was stirred for 5 h at ambient
temperature; then, 2.41 g (6.4 mmol) of ZrCl4(THF)2 was added
at -90 °C. The mixture was stirred for 48 h at room temper-
ature and then filtered through a glass frit (G4). The precipi-
tate was washed with 200 mL of hot toluene. The toluene
extract was evaporated to 1/2 of its initial volume; then, 100
mL of hexanes was added. The precipitate formed was
separated by filtration (G3), washed with 15 mL of hexanes,
and dried in a vacuum. Yield: 2.41 g (47%) of a yellow
crystalline solid of 22. Anal. Calcd for C42H56Cl2P2Zr: C, 64.26;
t
Hz, 2IÄ, 3/1-H in indenyl), 1.58 (d, J ) 14.7 Hz, 9H, Bu). 13C-
{1H} NMR (CD2Cl2): δ 130.5 (d, J ) 7.9 Hz), 129.7 (d, J )
17.2 Hz), 128.7, 127.7, 126.4, 126.1, 114.7 (d, J ) 42.7 Hz),
110.9 (d, J ) 33.6 Hz), 103.5 (d, J ) 7.6 Hz), 33.2 (d, J ) 15.3
Hz), 30.7 (d, J ) 16.8 Hz). 31P{1H} NMR (CD2Cl2): δ -12.0.
Complex 26. To a solution of 1.48 g (4.37 mmol) of 16 in
50 mL of ether was added 4.8 mL (8.75 mmol) of 1.84 M MeLi
in ether at -90 °C. This mixture was stirred for 12 h at
ambient temperature; then, 1.65 g (4.37 mmol) of ZrCl4(THF)2
was added at -90 °C. The mixture was stirred for 24 h at room
temperature and then evaporated to dryness. To the residue
was added 50 mL of toluene, and this mixture was stirred
additionally for 12 h. The orange slurry formed was filtered
through a glass frit (G4). The precipitate was washed with 50
mL of hot toluene. To the combined toluene extract was added
60 mL of hexanes. Crystallization of this solution at -30 °C
gave orange crystals of 26. Yield: 0.79 g (36%). Anal. Calcd
for C24H17Cl2PZr: C, 57.83; H, 3.44. Found: C, 58.11; H, 3.56.
1H NMR (C6D6): δ 7.53 (dq, J ) 8.5 Hz, J ) 1.0 Hz, 2H, 4/7-IÄ
in indenyl), 7.41-7.47 (m, 2H, 2,6-H in C6H5), 7.26 (dq, J )
8.5 Hz, J ) 1.0 Hz, 2H, 7/4-IÄ in indenyl), 6.98-7.20 (m, 3H,
3,4,5-H in C6H5), 6.96 (ddd, J ) 8.5 Hz, J ) 6.7 Hz, J ) 1.2
Hz, 2IÄ, 5/6-H in indenyl), 6.87 (ddd, J ) 8.5 Hz, J ) 6.7 Hz, J
) 1.2 Hz, 2IÄ, 5/6-H in indenyl), 6.21 (ddd, J ) 4.4 Hz, J ) 2.6
Hz, J ) 0.9 Hz, 2IÄ, 1/3-H in indenyl), 5.97 (m, 2IÄ, 3/1-H in
indenyl). 13C{1H} NMR (C6D6): δ 134.5, 134.1, 134.0, 131.2
(d, J ) 13.7 Hz), 129.2 (d, J ) 4.1 Hz), 127.3, 126.8, 126.5,
125.1, 125.0, 109.7 (d, J ) 38.2 Hz), 107.2 (d, J ) 27.5 Hz),
101.4 (d, J ) 7.6 Hz). 31P{1H} NMR (C6D6): δ -30.4.
1
H, 7.19. Found: C, 64.45; H, 7.26. H NMR (C6D6): δ 7.48-
7.54 (dd, J ) 6.5 Hz, J ) 3.1 Hz, 4H, 5,6-H in indenyl), 6.95-
7.02 (dd, J ) 6.5 Hz, J ) 3.1 Hz, 4H, 4,7-H in indenyl), 6.83
(s, 4H, 1,3-H in indenyl), 1.00-2.11 (m, 44H, N˜ o´). 13C{1H}
NMR (C6D6): δ 136.3, 128.7, 126.9, 125.1, 111.1 (d, J ) 8.2
Hz), 111.0 (d, J ) 8.2 Hz), 34.7, 34.5, 31.5 (d, J ) 13.7 Hz),
30.8 (d, J ) 12.2 Hz), 27.6 (d, J ) 11.7 Hz), 27.5 (d, J ) 11.7
Hz), 26.7. 31P{1H} NMR (C6D6): δ 12.8.
Complex 23. To a solution of 850 mg (3.26 mmol) of 23 in
35 mL of diethyl ether was added dropwise 1.30 mL of 2.5 M
(3.25 mmol) of nBuLi in hexanes under vigorous stirring at
-30 °C. The resulting mixture was slowly warmed to ambient
temperature and stirred for 3 h. To this solution cooled to -30
°C was added 615 mg (1.63 mmol) of ZrCl4(THF)2. The mixture
was stirred for 24 h at room temperature and then evaporated
to dryness. The product was extracted with 30 mL of toluene.
This toluene solution was filtered through a glass frit (G4).
Crystals precipitated at -30 °C from the filtrate were collected,
washed with 10 mL of cold toluene and 3 × 30 mL of hexanes,
and dried in a vacuum. Yield: 712 mg (64%). Anal. Calcd for

3034 Organometallics, Vol. 24, No. 12, 2005
Table 2. Crystallographic Data for 12, 13, 22, 25, and 27
Kazul’kin et al.
12
13‚(HCl)‚(H2O)
22
25
27
empirical formula
fw
C
27H23P3
C
11H16ClO2P
C42H56Cl2P2Zr
784.93
C22H21Cl2PZr
478.48
C26H30Cl2P2Zr
566.56
440.36
295(2)
246.66
temperature (K)
cryst size (mm)
cryst syst
space group
a, Å
110(2)
120(2)
120(2)
120(2)
0.50 × 0.50 × 0.20
orthorhombic
Pna21
29.717(10)
11.720(3)
6.498(2)
90
0.85 × 0.78 × 0.09
monoclinic
P21/c
0.40 × 0.25 × 0.15
0.50 × 0.25 × 0.10
monoclinic
P21/c
8.5662(16)
20.264(4)
11.765(2)
90
0.45 × 0.30 × 0.20
orthorhombic
P212121
10.1403(18)
11.598(2)
21.762(4)
90
triclinic
P1h
13.044(2)
10.5451(16)
9.0834(14)
90
102.569(3)
90
10.8977(11)
10.9949(15)
16.459(2)
78.178(4)
79.980(4)
76.357(4)
1859.3(4)
2
b, Å
c (Å)
R (deg)
â (deg)
90
90
102.098(4)
90
90
90
γ (deg)
V (Å3)
2263.1(12)
4
1219.5(3)
4
1997.0(7)
4
2559.5(8)
4
Z
dc (Mg m-3
F(000)
)
1.292
1.343
1.402
1.591
1.470
920
520
824
968
1160
µ (mm-1
)
0.275
0.423
0.555
0.902
0.776
θ range (deg)
2.21 to 25.00
-4 e h e 36
-14 e k e 2
-1 e 1 e 8
3557
2.51 to 32.32
-19 e h e 19
-15 e k e 15
-11 e l e 13
12 641
1.93 to 30.03
-15 e h e 15
-15 e k e 15
-23 e l e 23
22 427
2.01 to 30.03
-12 e h e 11
-27 e k e 28
-16 e l e 16
23 173
2.22 to 26.03
-12 e h e 12
-14 e k e 13
-26 e l e 26
18 501
index range
no. of rflns collected
no. of unique rflns
2553 [Rint
0.0180]
1670
)
4078 [Rint
0.0217]
3307
)
10760 [Rint
0.0302]
7379
)
5804 [Rint
0.0374]
4060
)
5003 [Rint
0.0538]
3717
)
no. of rflns with
I > 2σ(I)
R1; wR2 (I > 2σ(I))
R1; wR2 (all data)
no. of data/restraints/
params
0.0366; 0.0850
0.0829; 0.1009
2553/1/363
0.0504; 0.1293
0.0607; 0.1397
4078/0/200
0.0468; 0.0921
0.0686; 0.0982
10 760/0/658
0.0573; 0.1292
0.0824; 0.1430
5804/1/235
0.0702; 0.1692
0.0937; 0.1855
5003/42/452
GOF on F2
1.067
0.000
0.281/-0.333
1.073
0.001
1.595/-0.324
1.028
0.001
1.056/-0.733
0.887
0.001
2.091/-0.614
1.012
0.212
0.778/-0.855
max shift/error
largest diff peak/hole
(e Å-3
)
abs corr Tmax; Tmin
0.824; 0.635
0.928; 0.571
0.939; 0.856
0.802; 0.621
0.702; 0.862
Complex 27. To a solution of 713 mg (1.75 mmol) of 18 in
15 mL of toluene was added a solution of 642 mg (3.50 mmol)
of NaN(TMS)2 in 10 mL of toluene at ambient temperature.
This mixture was stirred for 24 h. The white precipitate formed
was filtered off (G3), washed with 3 × 30 mL of hexanes, and
dried in a vacuum. To a suspension of this sodium salt in 25
mL of diethyl ether was added 660 mg (1.75 mmol) of ZrCl4-
(THF)2. The resulting mixture was stirred for 48 h at ambient
temperature and then evaporated to dryness. The crude
product was extracted with 30 mL of toluene. The toluene
solution was filtered through a glass frit (G4), and the filtrate
was evaporated to ca. 10 mL. Crystals precipitated at -30 °C
were collected, washed with 3 × 30 mL of hexanes, and dried
in a vacuum. Yield: 520 mg (52%) of pure rac-complex (trans-
tBuPPBut). Anal. Calcd for C26H30Cl2P2Zr: C, 55.12; H, 5.34.
diffractometer and corrected for Lorentz and polarization
effects and for absorption.39 The structures were determined
by direct methods and by full matrix least-squares refinement
with anisotropic thermal parameters for non-hydrogen atoms.
The crystal 13 contains a solvate water molecule. One of the
four cyclohexyl substituents in 22 was disordered over two
sites with equal occupancies. The hydrogen atoms in 13 were
objectively localized in the difference Fourier map and refined
isotropically. The hydrogen atoms in 25 were placed in
calculated positions and refined using a riding model with fixed
thermal parameters. The hydrogen atoms in 22 were objec-
tively localized in the difference Fourier map and refined
isotropically except for the hydrogen atoms of disordered
cyclohexyl substituent, which were placed in calculated posi-
tions and refined using a riding model with fixed thermal
parameters. In the structure of 27, chlorine atoms, one of the
indenyl ligands, and the bridging tBu-P-P-tBu moiety were
found to be disordered over two positions with approximately
equal occupancies. In 27, all non-hydrogen atoms (except some
methyl carbons) were refined with anisotropic thermal pa-
rameters; all hydrogen atoms were placed in calculated posi-
tions and refined using a riding model. All calculations for 13,
22, 25, and 27 were carried out by use of the SHELXTL (PC
Version 5.10) program.40
1
Found: C, 55.28; H, 5.38. H NMR (CD2Cl2): δ 7.52 (m, 2H,
4/7-IÄ in indenyl), 7.42 (m, 2H, 7/4-IÄ in indenyl), 7.20 (m, 2IÄ,
5/6-H in indenyl), 7.12 (m, 2IÄ, 5/6-H in indenyl), 6.85 (m, 2IÄ,
1/3-H in indenyl), 6.62 (m, 2IÄ, 3/1-H in indenyl), 1.19 (t, J )
6.9 Hz, 18H, tBu). 13C{1H} NMR (CD2Cl2): δ 134.8, 130.9 (t, J
) 5.8 Hz), 128.3, 127.9, 127.6 (t, J ) 11.5 Hz), 127.0, 126.3,
116.8 (t, J ) 20.7 Hz), 106.5 (t, J ) 4.6 Hz), 32.8 (t, J ) 4.6
Hz), 31.1 (t, J ) 9.2 Hz). 31P{1H} NMR (CD2Cl2): δ -7.3.
X-ray Structural Determinations of 12, 13, 22, 25, and
27. Intensity measurements for 12 were carried out on an
Enraf-Nonius CAD4 diffractometer (Table 2). The structure
was solved by direct methods37 and refined by full matrix least-
squares on F2 with anisotropic thermal parameters for all non-
hydrogen atoms.38 Atom H(3) was found from difference
Fourier synthesis; other hydrogens were placed in calculated
positions. All H atoms were refined isotropically. Data for 13,
22, 25, and 27 were collected on a Bruker SMART 1000 CCD
Crystallographic data for the structures 12, 13, 22, 25, and
27 have been deposited with the Cambridge Crystallographic
Data Center, CCDC nos. 271236-271240, respectively, and
may be obtained free of charge from the Director CCDC, 12
Union Road, Cambridge CB2 1EZ, UK (fax: +44 1223 336033;
e-mail: deposit@ccdc.cam.ac.uk or www.ccdc.cam.ac.uk).
Olefin Polymerization Studies. Transition metal com-
pound (TMC) solutions (0.2 mmol/L) were typically prepared
(39) Sheldrick, G. M. SADABS, V2.01; Bruker/Siemens Area Detec-
tor Absorption Correction Program; Bruker AXS: Madison, WI, 1998.
(40) Sheldrick, G. M. SHELXTL, V5.10. Bruker AXS Inc.: Madison,
WI, 1997.
(37) Sheldrick, G. M. Acta Crystallogr. A 1990, A46, 467-473.
(38) Sheldrick, G. M. SHELXL-93, Program for the Refinement of
Crystal Structures; University of Go¨ttingen: Germany, 1993.

Zr Complexes with 2-R2P-Substituted Indenyl
Organometallics, Vol. 24, No. 12, 2005 3035
using toluene. Solvents, polymerization grade toluene, and
hexanes were supplied by ExxonMobil Chemical Co. and
thoroughly dried and degassed prior to use. 1-Octene (98%,
Aldrich) was dried by stirring over NaK overnight followed
by filtration through basic alumina (Brockman Basic 1, Ald-
rich). Polymerization grade ethylene was used and further
purified by passing it through a series of columns: 500 cm3
Oxyclear cylinder from Labclear (Oakland, CA) followed by a
500 cm3 column packed with dried 3 Å molecular sieves
(Aldrich), and a 500 cm3 column packed with dried 5 Å
molecular sieves (Aldrich). MAO (methylalumoxane, 10 wt %
in toluene) was purchased from Albemarle and was used as a
1 wt % in toluene solution. Micromoles of MAO reported in
the Experimental Section are based on the micromoles of
aluminum in MAO. The formula weight of MAO is 58.0 g/mol.
Polymerizations were conducted in an inert atmosphere (N2)
drybox using autoclaves equipped with an external heater for
temperature control, glass inserts (internal volume of reactor
) 23.5 mL), septum inlets, and a regulated supply of nitrogen
and ethylene and equipped with disposable PEEK mechanical
stirrers (800 rpm). The autoclaves were prepared by purging
with dry nitrogen at 110 or 115 °C for 5 h and then at 25 °C
for 5 h. The reactor was purged with ethylene. Toluene,
1-octene, and MAO were added via syringe at room temper-
ature and atmospheric pressure. The reactor was then brought
to process temperature (80 °C) and charged with ethylene to
process pressure (75 psig ) 517.1 kPa) while stirring at 800
rpm. The TMC (0.02 µmol) was added via syringe with the
reactor at process conditions. Amounts of reagents not specified
above are given in Table 1. Ethylene was allowed to enter
(through the use of computer-controlled solenoid valves) the
autoclaves during polymerization to maintain reactor gauge
pressure (( 2 psig). Reactor temperature was monitored and
typically maintained within (1 °C. Polymerizations were
halted by addition of approximately 50 psid O2/Ar (5 mol %
O2) gas mixture to the autoclaves for approximately 30 s. The
polymerizations were quenched after a predetermined cumula-
tive amount of ethylene had been added or for a maximum of
20 min polymerization time. The reactors were cooled and
vented. The polymer was isolated after the solvent was
removed in vacuo.
tion of 1.25 mg BHT/mL of TCB. Samples are cooled to 135 °C
for testing. Molecular weights (weight average molecular
weight (Mw) and number average molecular weight (Mn)) and
molecular weight distribution (MWD ) Mw/Mn), which is also
sometimes referred to as the polydispersity (PDI) of the
polymer, were measured by gel permeation chromatography
using a Symyx Technologies GPC equipped with evaporative
light scattering detector and calibrated using polystyrene
standards. Samples were run in TCB (135 °C sample temper-
atures, 160 °C oven/columns) using three Polymer Laboratories
PLgel 10 µm Mixed-B 300 × 7.5 mm columns in series.
Thermal analysis was measured on a Symyx Technologies
SAMMS (sensory array modular measurement system) instru-
ment that measures polymer melt temperatures via the 3 ω
technique. Samples for infrared analysis were subsequently
analyzed on a Brucker Equinox 55 FTIR spectrometer equipped
with Pikes MappIR specular reflectance sample accessory. For
ethylene-1-octene copolymers, the wt % copolymer is deter-
mined via measurement of the methyl deformation band at
∼1375 cm-1. The peak height of this band is normalized by
the combination and overtone band at ∼4321 cm-1, which
corrects for path length differences. The normalized peak
1
height is correlated to individual calibration curves from H
NMR data to predict the wt % copolymer content within a
concentration range of ∼2 to 35 wt % for octane-1. Typically,
R2 correlations of 0.98 or greater are achieved.
Acknowledgment. Financial support from Exxon-
Mobil Chemical Company, the International Science
and Technology Center (grant no. 1036/99), and the
President of the Russian Federation (grant no. MD-
340.2003.03) is gratefully acknowledged. A.V.C. thanks
the grant of The President of Russian Federation for
young scientists (MK-3697.2004.3) and Russian Science
Support Foundation. The authors thank Dr. David H.
McConville from ExxonMobil Chemical for fruitful dis-
cussions and polymerization experiments performed.
Supporting Information Available: Tables of crystal
data, data collection, structure solution and refinement pa-
rameters, atomic coordinates, anisotropic thermal parameters,
For analytical testing, polymer sample solutions were
prepared by dissolving polymer in 1,2,4-trichlorobenzene (TCB,
99+% purity, Aldrich) containing 2,6-di-tert-butyl-4-meth-
ylphenol (BHT, 99%, Aldrich) at 160 °C in a shaker oven for
approximately 3 h. The typical concentration of polymer in
solution is between 0.4 and 0.9 mg/mL with a BHT concentra-
1
and bond lengths and angles for 12, 13, 22, 25, and 27. H-
{13C} and 31P{1H} NMR spectra of compound 12. This material
is available free of charge via the Internet at http://pubs.acs.org.
OM050236H