Investigation of Zr-C, Zr-N, and potential agostic interactions in an organozirconium complex by experimental electron density analysis

Article abstract of DOI:10.1021/ja021133i

The crystal structure and electron density (ED) distribution of an imine coupling product with an open zirconocene, Zr(2,4-C₇H₁₁)[(i-Pr)NCHPhCH₂ CMe=CHCMe=CH₂] (C₇H₁₁ = dimethylpentadienyl), have been derived from accurate synchrotron X-ray diffraction measurements. The molecular structure reveals asymmetric coordination of Zr by the pentadienyl (2,4-C₇H₁₁ ligand (〈Zr-C〉 = 2.56(6) A), the butadiene fragment (〈Zr-C〉 = 2.43(5) A), and the amide nitrogen atom (Zr-N = 2.0312(5) A) of the second ligand. The study of the ED and its topological analysis affords new insight into the bonding and electronic structure of the title zirconium complex. The interactions between the metal center and the ligands are represented by a Zr-N bond path and one Zr-C bond path with each of the pentadienyl and butadiene moieties, contrary to the usually depicted global metal-ligand bonding. The butadiene and pentadienyl groups exhibit a polarization of the corresponding π-like ED in the C-Zr directions, indicating that the whole conjugated systems are nonetheless involved. The 4d atomic orbitals of Zr exhibit unusual populations according to ligand field considerations, which reveal a high degree of σ-donation from the conjugated π systems of both ligands. As deduced from numerical integration over the topologically defined atomic basins, the Zr to ligand charge transfer is 1.48 e to the C₁₇NH₂₄ ligand and 0.68 e to dimethylpentadienyl. Topological analysis of a short intramolecular Zr...(C,H) contact provides no indication of the presence of agostic interactions, despite a small Zr-N-C angle of 102.87(4)°. Thus, no bond path and BCP (bond critical point) of the ED are found in the Zr...(C,H) region, which would have provided evidence for such direct interactions, nor is there any evidence for charge accumulation between the Zr and H atoms, or for lengthening of the C-H bond involved in the putative interaction. These characteristics, similar to those in other distorted situations, may be common for other electron-deficient d⁰ complexes.

Full text of DOI:10.1021/ja021133i

Published on Web 01/29/2003
Investigation of Zr-C, Zr-N, and Potential Agostic
Interactions in an Organozirconium Complex by Experimental
Electron Density Analysis
Sebastien Pillet,†,§ Guang Wu,† Vichien Kulsomphob,‡ Benjamin G. Harvey,‡
Richard D. Ernst,*,‡ and Philip Coppens*,†
Contribution from the Department of Chemistry, UniVersity of New York at Buffalo,
Buffalo, New York 14260, and Department of Chemistry, UniVersity of Utah,
Salt Lake City, Utah 84112
Received August 30, 2002 ; E-mail: ernst@chemistry.chem.utah.edu, coppens@acsu.buffalo.edu
Abstract: The crystal structure and electron density (ED) distribution of an imine coupling product with an
open zirconocene, Zr(2,4-C7H11)[(i-Pr)NCHPhCH2CMedCHCMedCH2] (C7H11 ) dimethylpentadienyl), have
been derived from accurate synchrotron X-ray diffraction measurements. The molecular structure reveals
asymmetric coordination of Zr by the pentadienyl (2,4-C7H11) ligand ( Zr-C ) 2.56(6) Å), the butadiene
fragment ( Zr-C ) 2.43(5) Å), and the amide nitrogen atom (Zr-N ) 2.0312(5) Å) of the second ligand.
The study of the ED and its topological analysis affords new insight into the bonding and electronic structure
of the title zirconium complex. The interactions between the metal center and the ligands are represented
by a Zr-N bond path and one Zr-C bond path with each of the pentadienyl and butadiene moieties, contrary
to the usually depicted global metal-ligand bonding. The butadiene and pentadienyl groups exhibit a
polarization of the corresponding π-like ED in the C-Zr directions, indicating that the whole conjugated
systems are nonetheless involved. The 4d atomic orbitals of Zr exhibit unusual populations according to
ligand field considerations, which reveal a high degree of σ-donation from the conjugated π systems of
both ligands. As deduced from numerical integration over the topologically defined atomic basins, the Zr
to ligand charge transfer is 1.48 e to the C17NH24 ligand and 0.68 e to dimethylpentadienyl. Topological
analysis of a short intramolecular Zr‚‚‚(C,H) contact provides no indication of the presence of agostic
interactions, despite a small Zr-N-C angle of 102.87(4)°. Thus, no bond path and BCP (bond critical
point) of the ED are found in the Zr‚‚‚(C,H) region, which would have provided evidence for such direct
interactions, nor is there any evidence for charge accumulation between the Zr and H atoms, or for
lengthening of the C-H bond involved in the putative interaction. These characteristics, similar to those in
other distorted situations, may be common for other electron-deficient d0 complexes.
Introduction
terms of chemistry, their coupling reactions with alkynes have
proven to be particularly interesting, in several cases leading
Metal pentadienyl compounds have been found to display a
great deal of diversity in their structural nature as well as a rich
variety of reaction chemistry, including coupling reactions,
naked metal chemistry, and applications in metal film deposi-
tions, syntheses of new materials, and catalysis.1 Open and half-
open titanocenes and zirconocenes have provided especially
valuable insight in this regard, most notably by demonstrating
that pentadienyl ligands may be both more strongly bound and
more reactive than their cyclopentadienyl counterparts.2-4 In
to complexes in which C-C single bonds have been constructed
in bonding proximity to titanium,1 and agostic interactions have
been proposed on the basis of lengthened C-C bonds, dramati-
cally reduced 13C-13C coupling constants, and supporting
theoretical studies.5
In a related reaction of an open zirconocene with an imine,
a Zr-N-C-H group has been generated with the unusually
small Zr-N-C angle of 102.87(4)°, as compared to a value of
130.4(4)° in a similar titanium complex.6 Although a (C-H)‚
‚‚Zr interaction was first suspected, the observation of a rather
normal C-H coupling constant, ca. 125 Hz, did not provide
support for this. However, the observation in another complex
that a Ti interaction with a C-C bond could occur even in the
presence of a C-H bond,1 together with the fact that other
complexes are known in which a metal center interacts
† University of New York at Buffalo.
‡ University of Utah.
§ Present address: Laboratoire de Cristallographie et Mode´lisation des
Mate´riaux Mine´raux et Biologiques, LCM3B, UMR 7036, UHP Nancy I,
54506 Vandoeuvre les Nancy cedex, France.
(1) Ernst, R. D. Comments Inorg. Chem. 1999, 21, 285-325.
(2) Hyla-Kryspin, I.; Waldman, T. E.; Melendez, E.; Trakarnpruk, W.; Arif,
A. M.; Ziegler, M. L.; Ernst, R. D.; Gleiter, R. Organometallics 1995, 14,
5030-5040.
(3) Wilson, A. M.; West, F. G.; Rheingold, A. L.; Ernst, R. D. Inorg. Chim.
Acta 2000, 300-302, 65-72.
(5) Tomaszewski, R.; Hyla-Kryspin, I.; Mayne, C. L.; Arif, A. M.; Gleiter,
R.; Ernst, R. D. J. Am. Chem. Soc. 1998, 120, 2959-2960.
(6) Tomaszewski, R.; Lam, K.-C.; Rheingold, A. L.; Ernst, R. D. Organome-
tallics 1999, 18, 4174-4182.
(4) Kulsomphob, V.; Harvey, B. G.; Arif, A. M.; Ernst, R. D. Inorg. Chim.
Acta 2002, 334, 17-24.
9
10.1021/ja021133i CCC: $25.00 © 2003 American Chemical Society
J. AM. CHEM. SOC. 2003, 125, 1937-1949
1937

A R T I C L E S
Pillet et al.
preferentially with a Si-C bond rather than with a C-H bond,7,8
raised the possibility of a (C-N)‚‚‚Zr interaction in the imine
coupling product, perhaps in conjunction with a (C-H)‚‚‚Zr
interaction. As the nature of the bonding in various agostic and
σ-bond complexes is directly and fundamentally related to the
oxidative addition process,9,10 and therefore also to many other
types of important bond activation reactions11 and to processes
of major technical significance (e.g., olefin polymerizations12-17),
an understanding of the interactions which characterize such
species is clearly desirable.
cyclopentadienyl, diene, and alkyl fragments.5 Antipin et al.29
have analyzed the experimental ED of vanadocene, and, more
generally, the nature of interactions in π-ligands η2 coordinated
to a metal atom has been investigated in a series of studies by
Macchi et al.30,31
The goals of the study presented here are to probe the
electronic nature of the interactions between zirconium and
several key classes of ligands and to investigate the origin of
the short intramolecular Zr‚‚‚H and Zr‚‚‚C contacts present in
the title complex, which may represent an agostic interaction,
in analogy with those found in a number of other Zr com-
plexes.32,33 The concepts of the charge density analysis, applied
here and in previous studies (see, for example, Scherer et al.34),
allow the characterization of the nature of such interactions.
To our knowledge, this work represents the first ED study and
topological analysis of a zirconium complex, as well as the first
experimental examination of metal coordination involving diene,
open dienyl, and amide ligands.
Experimental and theoretical electron density (ED) analysis
has become an attractive tool to investigate the bonding and
electronic structure of metal-based compounds.18,19 Insight into
the nature of metal-ligand interactions and metal-metal
bonding has been obtained, especially in the framework of the
“quantum theory of atoms in molecules” (QTAIM).20 The
physical and chemical applications range from purely organo-
metallic systems21 to intermetallic22 and metallic clusters.23,24
Such studies have been mostly restricted to first-row transition
metal complexes, as anharmonic thermal motion at all but the
lowest experimental temperatures complicates the analysis of
heavier transition metal complexes. The use of synchrotron
radiation allows measurements on very small crystal samples
at short wavelengths, thus drastically decreasing sources of
uncertainty such as absorption or extinction.25 As shown here,
the study of heavier-atom containing systems is now a realistic
possibility.
This paper is divided into four parts. Following this introduc-
tion, the Experimental Details section describes the X-ray
diffraction measurements and the data reduction and charge
density refinement. The crystal structure and ED results are
discussed in the Results section, with a focus on the metal-
ligand interactions and the putative agostic Zr‚‚‚H bond.
Concluding remarks are given in the final section.
Experimental Details and Electron Density Refinement
Synthesis and Spectroscopic Characterization. All synthetic and
spectroscopic procedures were carried out under a nitrogen atmosphere
in Schlenk apparatus or in a glovebox. Zr(2,4-C7H11)2(PMe3) was
prepared by a published procedure,35 while organic reagents were
purchased commercially. Solvents were dried and degassed by distil-
lation from sodium/benzophenone under a nitrogen atmosphere.
Spectroscopic studies were carried out as previously described.36
Zr(2,4-C7H11)[(i-Pr)NCHPhCH2CMedCHCMedCH2]. To a mag-
netically stirred solution of 0.60 g (1.7 mmol) of Zr(2,4-C7H11)2(PMe3)
(C7H11 ) dimethylpentadienyl) in 50 mL of THF under nitrogen at
-78 °C was added 0.50 mL (3.4 mmol) of N-benzylidene isopropyl-
amine. The initial green solution was allowed to warm to room
temperature and was stirred for 4 h. A gradual color change from dark
green to dark red was observed. The solvent was removed in vacuo,
and the crude product was extracted with three 20 mL portions of
pentane. The extracts were filtered through a Celite pad on a coarse
frit and concentrated to ca. 15 mL. The solution was placed into a
-30 °C freezer overnight, yielding large, dark red cubic crystals (0.33
g, 45% yield, mp 91-94 °C). This compound is very air- and moisture-
sensitive, but it can be stored under nitrogen indefinitely without
apparent decomposition. Occasionally, the sample can be contaminated
by a small amount of starting material which is easily removed by
fractional crystallization. Smaller crystals, more suitable for the electron
density analysis, were obtained by cooling a concentrated solution in
Metallocenes have already been the subject of several ED
studies. A topological analysis of the ED of group 2 metal-
locenes has been reported by Bytheway et al.26 from Hartree-
Fock (HF) and density functional theory (DFT) methods. Bader
et al.27,28 introduced and used the concept of localization and
delocalization indexes to investigate bonding between Ti and
(7) Klooster, W. T.; Brammer, L.; Schaverien, C. J.; Budzelaar, P. H. M. J.
Am. Chem. Soc. 1999, 121, 1381-1382.
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(9) Kubas, G. J.; Unkefer, C. J.; Swanson, B. I.; Fukushima, E. J. Am. Chem.
Soc. 1986, 108, 7000-7009.
(10) Kubas, G. J. Metal Dihydrogen and σ-Bond Complexes; Kluwer Academic/
Plenum: New York, 2001.
(11) Stahl, S. S.; Labinger, J. A.; Bercaw, J. E. Inorg. Chem. 1998, 37, 2422-
2431.
(12) Yang, X.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1994, 116, 10015-
10031.
(13) Resconi, L.; Piemontesi, F.; Franciscono, G.; Abis, L.; Fiorani, T. J. Am.
Chem. Soc. 1992, 114, 1025-1032.
(14) Eshuis, J. J. W.; Tan, Y. Y.; Meetsma, A.; Teuben, J. H.; Renkema, J.;
Evens, G. G. Organometallics 1992, 11, 362-369.
(15) Schmidt, G. F.; Brookhart, M. J. Am. Chem. Soc. 1985, 107, 1443-1444.
(16) Ivin, K. J.; Rooney, J. J.; Stewart, C. D.; Green, M. L. H.; Mahtab, R. J.
Chem. Soc., Chem. Commun. 1978, 604-606.
(17) Turner, H. W.; Schrock, R. R.; Fellmann, J. D.; Holmes, S. J. J. Am. Chem.
Soc. 1983, 105, 4942-4950.
(18) Coppens, P. X-ray Charge Densities and Chemical Bonding; Oxford
University Press: New York, 1997.
(19) Koritsanszki, T. S.; Coppens, P. Chem. ReV. 2001, 101, 1583-1628.
(20) Bader, R. F. W. Atoms in Molecules: A Quantum Theory; Clarendon
Press: New York, 1990.
(29) Antipin, M. Y.; Lyssenko, K. A.; Boese, R. J. Org. Chem. 1996, 61, 259-
262.
(21) Pillet, S.; Souhassou, M.; Mathoniere, C.; Lecomte, C., to be published.
(22) Gavoille, G.; Hansen, N. K.; Welter, R.; Malaman, B.; Krane, H. G.; Herzig,
P. J. Phys.: Condens. Matter 2000, 12, 2667-2679.
(23) Macchi, P.; Proserpio, D. M.; Sironi, A. J. Am. Chem. Soc. 1998, 120,
13429-13435.
(30) Macchi, P.; Proserpio, D. M.; Sironi, A. J. Am. Chem. Soc. 1998, 120,
1447-1455.
(31) Macchi, P.; Schultz, A. J.; Larsen, F. K.; Iversen, B. B. J. Phys. Chem. A
2001, 105, 9231-9242.
(32) Meier, R. J.; van Doremaele, G. H. J.; Iarlori, S.; Buda, F. J. Am. Chem.
Soc. 1994, 116, 7274-7281.
(24) Macchi, P.; Garlaschelli, L.; Martinengo, S.; Sironi, A. J. Am. Chem. Soc.
1999, 121, 10428-10429.
(33) Woo, T. K.; Fan, L.; Ziegler, T. Organometallics 1994, 13, 2252-2261.
(34) Scherer, W.; Hieringer, W.; Spiegler, M.; Sirsch, P.; McGrady, G. S.;
Downs, A. J.; Haaland, A.; Pedersen, B. Chem. Commun. 1998, 2471-
2472.
(25) Coppens, P.; Wu, G.; Volkov, A.; Abramov, Y.; Zhang, Y.; Fullagar, W.
K.; Ribaud, L. Trans. Am. Crystallogr. Assoc. 1999, 34, 51-64.
(26) Bytheway, I.; Popelier, P. L. A.; Gillespie, R. J. Can. J. Chem. 1996, 74,
1059-1071.
(35) Waldman, T. E.; Stahl, L.; Wilson, D. R.; Arif, A. M.; Hutchinson, J. P.;
Ernst, R. D. Organometallics 1993, 12, 1543-1552.
(36) Newbound, T. D.; Stahl, L.; Ziegler, M. L.; Ernst, R. D. Organometallics
1990, 9, 2962-2972.
(27) Fradera, X.; Austen, M. A.; Bader, R. F. W. J. Phys. Chem. A 1999, 103,
304-314.
(28) Bader, R. F. W.; Matta, C. F. Inorg. Chem. 2001, 40, 5603-5611.
9
1938 J. AM. CHEM. SOC. VOL. 125, NO. 7, 2003

Interactions in an Organozirconium Complex
A R T I C L E S
Table 1. Crystallographic Data and Experimental Details (Tmin and
Tmax are the Minimum and Maximum Transmission Coefficients)
a/b/c (Å)
8.5981(4)/9.3991(5)/27.0670(9)
97.482(4)/2168.8(2)/4
P21/n/monoclinic
16/0.6361
ω
0.3
â (deg)/V (Å3)/Z
space group/crystal system
temperature (K)/wavelength (Å)
scan method
frame width (deg)
exposure time per frame (s)
no.measured/
7 (at 2θ ) 27°)/10 (at 2θ ) 65°)
43 676/13 948
independent reflections
range of h/k/l
-20 < h < 19, 0 < k < 20,
0 < l < 43
R
int (I) (%)
2.78
(sin θ/λ) max (Å-1
)
1.17
3.0
2.16/0.85/0.87
mean redundancy
µ (mm-1)/Tmin/Tmax
pentane to -60 °C overnight. All NMR assignments were corroborated
utilizing HETCOR 2D NMR techniques.
1H NMR (benzene-d6, ambient): δ 7.1-7.4 (m, 5H, phenyl), 4.97
(s, 1H), 4.91 (s, 1H), 4.51 (d, 1H, C(H)(C6H5), J ) 6.5 Hz), 3.90 (s,
1H), 3.26 (s, 1H), 2.90 (dd, 1H), 2.45 (septet, 1H, C(H)(CH3)2, J )
6.6 Hz), 2.41 (d, 1H, J ) 6.5 Hz), 2.20 (dd, 1H, J ) 6.0, 1.0 Hz), 2.17
(s, 1H), 2.16 (s, 3H, CH3), 2.09 (s, 3H, CH3), 1.85 (s, 3H, CH3), 1.61
(d, 1H, J ) 2.5 Hz), 1.52 (s, 3H, CH3), 1.42 (s, 2H), 0.81 (2d, 6H,
CH3 on NC(H)(CH3)2, J ) 6.0 Hz).
Figure 1. ORTEP view and atom numbering scheme of Zr(2,4-C7H11)(NMe2-
CHPhCH2CMedCHCMedCH2). Ellipsoids drawn at the 50% level prob-
ability and arbitrary radius for H24. H atoms (except H24) omitted for
clarity.
13C NMR (benzene-d6, ambient): δ 150.0 (s, 1C on phenyl), 137.7
(s, 1C), 136.3 (s, 1C), 126-130 (m, 5C, phenyl), 118.9 (s), 116.7 (d,
1C, J ) 153 Hz), 91.8 (d, 1C, J ) 163 Hz), 83.4 (s, 1C), 81.2 (t, 1C,
J ) 157 Hz), 80.7 (t, 1C, J ) 157 Hz), 72.4 (d, (C6H5)CH, J ) 131
Hz), 52.0 (t, 1C, J ) 150 Hz), 46.1 (d, CH(CH3)2, J ) 128 Hz), 45.3
(t, 1C, J ) 128 Hz), 32.4, 30.3, 29.4, 28.4, 25.2, 22.5 (6q, 6CH3, J )
ca. 125 Hz).
Structure and Charge Density Refinements. To get a starting
molecular geometry for the subsequent ED fitting, the crystal structure
was solved in the P21/n space group by direct methods and refined by
full matrix least-squares on F 2 using SHELX.40 Non-hydrogen atoms
were refined anisotropically using all reflections (I > 0). Hydrogen
atoms were located in Fourier difference maps and refined isotropically
(R ) 3.32%, Rw ) 5.94%, and GOF ) 0.757). ORTEP views of the
molecular structure and the crystal packing are presented in Figures 1
and 2, while a detailed analysis of the crystal structure is given in the
next section. This independent atom model is referred to below as model
I.
Anal. Calcd for C24H35NZr: C, 67.23; H, 8.23; N, 3.26. Found: C,
67.07; H, 8.12; N, 3.08.
Data Collection and Reduction. An irregularly shaped single crystal
of dimensions 0.11 × 0.10 × 0.06 mm3 was mounted on a Huber four-
cycle diffractometer at the SUNY X3A1 beamline at the National
Synchrotron Light Source at Brookhaven National Laboratory. The
sample was cooled to ∼16 K using an open helium gas-flow system.37
Data were collected by the æ-scan method (frame width ∆æ ) 0.3°)
using two different detector settings. Low angle data were measured
at a detector position of 2θ ) 27°, using a 7 s per frame exposure time
(33 483 reflections on 1800 frames). To ensure high-resolution, crucial
for an accurate charge density study, 502 frames (10 193 reflections)
were measured using a detector position of 2θ ) 65° and 10 s exposure
time. The data were corrected for oblique incidence of the reflected
beams on the phosphor of the SMART6000 CCD detector.38
For heavy atom containing crystals, the data accuracy can be strongly
affected by absorption effects, which have been very much reduced in
the present experiment by the small sample size. Because the crystal
faces could not be unambiguously indexed, an empirical absorption
correction was performed assuming a mean spherical crystal of 0.05
mm radius (µ ) 2.16 mm-1) and fitting the transmission surface using
SORTAV.39 The resulting minimum and maximum transmission
coefficients are Tmin ) 0.85 and Tmax ) 0.87. Next 43 676 reflections
were reduced and merged in Laue group 2/m to give 13 948 unique
reflections up to a resolution of S ) sinθ/λ ) 1.17 Å-1. The low internal
agreement indices (Rint ) 2.78% (2.81% before absorption correction)
and Rw ) 3.20%, redundancy ) 3.0) support the good quality and
consistency of the merged data set. Crystallographic and data collection
details are reported in Table 1.
In a following refinement, the ED was fitted using the multipole
model,41 according to the Hansen and Coppens formalism as imple-
mented in the MOLLY program.42 In this model, the ED is described
as a superposition of nonspherical pseudoatoms (eq 1):
lmax
+l
F(br) ) Fcore(r) + Pvκ3Fval(κr) +
κ′3Rin(κ′r)
Plm(dlm((θ,æ)
∑
∑
l)0
m)0
(1)
where Fcore(r) and Fval(r) correspond, respectively, to spherically
averaged Hartree-Fock core and valence electron densities for isolated
atoms. κ and κ′ are contraction-expansion parameters, and Pv is the
electron population of the corresponding atomic valence shell. Real
spherical harmonics (dlm() describe the anisotropy of the valence ED
through the multipole population parameters Plm(. The atomic core
ED Fcore(r) was fixed during the ED fitting, assuming no perturbation
due to chemical bonding.
For the N, C, and H atoms, the core and valence atomic spherical
electron densities were calculated from Clementi Hartree-Fock wave
functions for ground-state isolated atoms.43 The following coefficients
[(nl ) 2, 2, 3, úl ) 3.00 Bohr-1) for N, (nl ) 2, 2, 3, úl ) 3.14 Bohr-1
)
for C, and (nl ) 2, úl ) 2.26 Bohr-1) for H] were used for the Slater-
n
-ê r
l
type radial functions Rin(r) ) (êln +3/(nl + 2)!)r e . The multipolar
l
l
expansion was limited to the orders lmax ) 3 (octupole) for N and C,
(37) Ribaud, L.; Wu, G.; Zhang, Y.; Coppens, P. J. Appl. Crystallogr. 2001,
34, 76-79.
(40) Sheldrick, G. M. SHELXL93; University of Go¨ttingen: Germany, 1993.
(41) Stewart, R. F. J. Chem. Phys. 1973, 58, 1668-1676.
(42) Hansen, N. K.; Coppens, P. Acta Crystallogr., Sect. A 1978, 34, 909-921.
(43) Clementi, E.; Roetti, C. At. Data Nucl. Data Tables 1974, 14, 177-478.
(38) Wu, G.; Rodrigues, B.; Coppens, P. J. Appl. Crystallogr. 2002, 35, 356-
359.
(39) Blessing, R. H. J. Appl. Crystallogr. 1989, 22, 396-397.
9
J. AM. CHEM. SOC. VOL. 125, NO. 7, 2003 1939

A R T I C L E S
Pillet et al.
Figure 2. Crystal packing. π-π intermolecular contacts between dimethylpentadienyl anions are depicted as dashed lines.
Table 2. Atomic Positions (Fractional Coordinates) and Ueq (Ueq
) (U11 + U22 + U33)/3 in Å2) Values
and lmax ) 1 (dipole) for H. The anomalous dispersion coefficients
were taken from Kissel et al.,44 as computed from relativistic Hartree-
Fock Slater wave functions. Only one (κ, κ′) set was used for the H
atoms, with κ′ for the dipolar functions fixed at unity. Chemical
constraints were also applied to the other κ and κ′ parameters, including
three different constraints for the C atoms (one each for the phenyl C
atoms, the sp2, and sp3 C atoms). Extinction effects were not significant.
atom
x
y
z
U
eq
Zr
N
C1
C2
C3
C4
C5
C6
0.990868(6)
0.96722(6)
0.85918(8)
0.84358(7)
0.97093(7)
1.13688(7)
1.21119(7)
0.67939(8)
1.23901(8)
1.14064(7)
1.00907(7)
0.84788(7)
0.77430(7)
1.04715(8)
0.59968(8)
0.82266(8)
0.87564(7)
1.11223(7)
1.22476(8)
1.08358(8)
0.73966(7)
0.67061(7)
0.54780(8)
0.49034(8)
0.55660(8)
0.68081(8)
0.193780(6)
0.40568(5)
-0.03849(7)
0.07307(7)
0.15434(7)
0.14226(7)
0.06045(7)
0.12219(8)
0.24569(8)
0.15113(7)
0.05419(7)
0.09247(7)
0.22687(6)
-0.10369(7)
0.21761(7)
0.36622(7)
0.48301(6)
0.46495(6)
0.52955(7)
0.56714(8)
0.57105(7)
0.67635(7)
0.76106(7)
0.74073(7)
0.63463(7)
0.55108(7)
0.127798(2)
0.13947(2)
0.08687(2)
0.05278(2)
0.03692(2)
0.05147(2)
0.09074(2)
0.03233(2)
0.02678(2)
0.20552(2)
0.20341(2)
0.19262(2)
0.17984(2)
0.20690(2)
0.16101(2)
0.20732(2)
0.17231(2)
0.12439(2)
0.16714(2)
0.07984(2)
0.14584(2)
0.17304(2)
0.15034(2)
0.10002(2)
0.07288(2)
0.09565(2)
0.00688(2)
0.0102(2)
0.0125(2)
0.0103(2)
0.0103(2)
0.0105(2)
0.0128(2)
0.0150(3)
0.0151(2)
0.0114(2)
0.0102(2)
0.0100(2)
0.0101(2)
0.0141(3)
0.0141(3)
0.0111(2)
0.0095(2)
0.0098(2)
0.0138(3)
0.0151(3)
0.0099(2)
0.0115(2)
0.0131(3)
0.0133(3)
0.0134(3)
0.0121(2)
In molecular complexes such as the zirconocenes, the Zr atom can
adopt valence states varying from 0 to IV. Therefore, different starting
hypotheses of the electron configuration corresponding to neutral
zirconium ((Kr)5s24d2), the Zr2+ ion ((Kr)4d2 and (Kr)5s2), and the
Zr4+ ion were tested, even though a 2+ or 4+ formal charge is expected
for the present complex, depending on whether the diene ligand is
formally neutral or dianionic (enediyl). For each model, Zr core and
spherical valence atomic scattering factors were derived from relativistic
wave functions of Zr, as tabulated by Macchi and Coppens.45 The radial
scattering factors of the 4d and 5s electrons of zirconium differ less
than the corresponding 3d and 4s scattering of the first row transition
metal elements, preventing a clear distinction between the spherical
components of the two shells. Because of the high correlation between
the corresponding population parameters, one monopole was assigned
to the 5s electrons, and one monopole was assigned to the 4d electrons
without refining both simultaneously. In the following, the starting
configurations (Kr)5s24d2 and (Kr)4d2 correspond to models III and
IV, respectively. In model III, the monopole population corresponding
to the 5s electrons was kept fixed at 2 electrons, whereas the population
of the monopole describing the spherical 4d shell was varied during
the refinement procedure. In model IV, the monopole population
corresponding to the 5s electrons was fixed at zero, and the second
monopole population corresponding to the 4d electrons was fitted. The
multipole expansion was limited to the order lmax ) 4 (hexadecapole)
with the following radial exponents (nl ) 6, 6, 6, 6, úl ) 6.00).
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
C22
C23
C24
both charge density and conventional (positional and thermal) param-
eters were refined.
Chemical constraints were applied to the hydrogen atom valence
ED (identical Pv and Plm( parameters); these constraints were relaxed
at the end of refinement. Tables 2 and 3 summarize atomic positions
and selected bond lengths and angles at the end of multipolar refinement
(model III). The Hirshfeld rigid bond test47 indicates that a reasonable
deconvolution between ED and thermal smearing effects was achieved.
The mean difference between the mean-square displacements of two
bonded atoms along the bond is 0.0011 Å2 for C-C and C-N bonds.
The Zr-C and Zr-N bonds present a higher mean difference (0.0040
Å2), as expected for nonsimilar weight atoms.
The agreement factors are summarized in Table 4. The different
refinements agree on the essential features of the electron distribution.
In the following, we will only discuss the results of model III, which
we believe to be the most reliable. The residual density for model III
is shown in Figure 3. The low residual density attests to the quality of
the modeled ED.
The starting atomic positions were taken from the SHELX refine-
ment, and the C-H bond lengths were normalized to the usual neutron
values (1.08 Å)46 by shifting the hydrogen atoms along the C-H
directions. The positions and thermal parameters for non-hydrogen
atoms were first refined against the high angle data (S > 0.8 Å-1) to
deconvolute thermal smearing effects and ED. The valence ED was
then fitted against low angle data (S < 0.8 Å-1) in successive cycles
on Pv, κ, Plm(, and κ′ parameters, while constraining the electroneu-
trality of the crystal, until convergence was reached. In the final cycles,
(44) Kissel, L.; Zhou, B.; Roy, S. C.; Sen Gupta, S. K.; Pratt, R. H. Acta
Crystallogr., Sect. A 1995, 51, 271-288 (http://www-phys.llnl.gov/Research/
scattering/index.html).
(45) Macchi, P.; Coppens, P. Acta Crystallogr., Sect. A 2001, 57, 656-662.
(46) Allen, F. H. Acta Crystallogr., Sect. B 1986, 42, 515-522.
(47) Hirshfeld, F. L. Acta Crystallogr., Sect. A 1976, 32, 239-244.
9
1940 J. AM. CHEM. SOC. VOL. 125, NO. 7, 2003

Interactions in an Organozirconium Complex
A R T I C L E S
Table 3. Selected Bond Lengths (Å) and Angles (deg)
Bond Lengths
Zr-C1
2.6359(6)
2.5189(6)
2.4714(6)
2.5988(6)
2.5808(7)
2.4604(6)
1.3918(9)
1.4454(9)
1.4344(9)
1.4479(8)
1.4248(9)
1.5199(9)
1.4564(8)
3.9777(8)
3.8741(8)
3.7436(9)
3.4944(8)
Zr-C8
Zr-C9
Zr-C10
Zr-C11
Zr-N
2.3535(6)
2.4190(6)
2.4613(6)
2.4963(6)
2.0309(5)
Zr-C2
Zr-C3
Zr-C4
Zr-C5
Zr‚‚‚H24
C1-C2
C2-C3
C3-C4
C8-C9
C9-C10
C9-C12
N-C15
C1‚‚‚C3a
C1‚‚‚C4a
C2‚‚‚C3a
C2‚‚‚C4a
C4-C5
1.3971(9)
1.5195(9)
1.5217(9)
1.4347(8)
1.5239(9)
1.5366(9)
1.4710(8)
4.0509(8)
3.595(1)
C2-C6
C4-C7
C10-C11
C11-C13
C11-C14
N-C16
plex,36,50 in which the zirconium center is coordinated by a
dimethylpentadienyl ligand and by the butadiene fragment of
the C17NH24 ligand (Figure 1). The coordination sphere of Zr
is at least formally completed by the N atom of the C17NH24
ligand with a Zr-N distance of 2.0312(5) Å. The Zr-C
distances range from 2.3531(6) to 2.6358(6) Å with a mean
value of 2.50(8) Å, in line with those reported for other Zr-
C2‚‚‚C5a
C3‚‚‚C3a
C3‚‚‚C4a
C3‚‚‚C5a
3.7119(8)
4.1301(8)
Bond Angles
125.71(6)
129.91(6)
116.92(5)
131.18(6)
113.78(5)
C1-C2-C3
C2-C3-C4
C5-C4-C7
C9-C10-C11
C14-C11-C13
C3-C4-C5
C1-C2-C6
C8-C9-C10
C8-C9-C12
126.33(6)
118.37(6)
125.68(6)
116.81(6)
(2,4-C7H11)2 compounds,35 Zr(2,4-C7H11)2(PEt3) ( Zr-C
)
2.49(3) Å), Zr(2,4-C7H11)2(CO) ( Zr-C ) 2.45(2) Å), Zr(2,4-
C7H11)2(CO)2 ( Zr-C ) 2.52(3) Å), Zr(C5H7)2(dmpe) ( Zr-
C ) 2.49(3) Å).51
a 2 - x, -y, -z.
The mean distance to the Zr atom is longer for the 2,4-C7H11
ligand (2.56(6) Å) than for the butadiene moiety of the second
ligand (2.43(5) Å), the zirconium atom thus being displaced
toward the butadiene. A difference in terms of bond strength is
therefore expected and confirmed by the following ED analysis.
The short Zr-N contact causes the butadiene and pentadienyl
ligands to be nonparallel, with an angle of 33.49(4)° between
the corresponding best planes.
Table 4. Agreement Factors for the Different Refinement Models
model
N
par
R (%)
Rw (%)
GOF
I (SHELX)
375
441
1211
1211
3.37
3.15
2.71
2.77
6.04
2.33
1.58
1.64
0.77
1.12
0.76
0.79
II (spherical)
III (multipolar)
IV (multipolar)
Results
The pentadienyl group is almost planar, with a root-mean-
square deviation from the best plane of 0.04 Å, the C6 and C7
atoms being displaced from the plane by 0.241(1) and 0.066(1)
Å, respectively. The central C2-C3 and C3-C4 bond lengths
differ from the C1-C2 and C4-C5 bond lengths by 0.045(3)
Å, revealing a difference in bond orders in the conjugated system
as, for example, in Zr(2,4-C7H11)2(CO)2 and Zr(2,4-C7H11)2-
(CO),35 which arises from a contribution from resonance
structure 2. Similarly, the butadiene fragment of the C17NH24
Synthesis and Characterization. The reaction of Zr(2,4-
C7H11)2(PMe3) with 1 equiv of N-benzylidene isopropylamine
leads to a selective 1:1 coupling reaction (eq 2). The somewhat
Zr(2,4-C7H11)2(PMe3) + (Ph)(H)CdN(i-Pr) f
Zr(2,4-C7H11)((i-Pr)NC(H)(Ph)CH2CMedCHCMedCH2)
(2)
air-sensitive product was readily isolated as a crystalline solid
and fully characterized through analytical and spectroscopic data.
These data were fully consistent with the expected formulation
1
of such a species (1). In particular, the complexities of the H
and 13C NMR spectra were consistent with the lack of any
symmetry, and one of the four CH2 groups displayed a low
J(13C-H) value, 128 Hz versus 150-157 Hz for the other three,
indicative of the former’s expected sp3 hybridization brought
about by its coupling to the imine carbon atom.48 On the basis
of the above data, then, complex 1 was expected to possess
η5-dienyl, η4-diene, and π-amide coordination, leading straight-
forwardly to its formulation as a 16-electron complex, analogous
to related titanium complexes.6,49
ligand exhibits an almost perfect planarity with a root-mean-
square deviation from the best plane of only 0.01 Å, C12 and
C13 being out of the plane by 0.228(1) and 0.256(1) Å,
respectively. The C-C bond lengths in the butadiene fragment
(1.4479(8), 1.4248(9), and 1.4347(8) Å for C8-C9, C9-C10,
and C10-C11, respectively) do not exhibit single/double bond
alternation. This is consistent with significant contributions from
both η4-diene (3) and η4-enediyl (4) resonance forms, the latter
of which would be expected to lead to shorter Zr-C distances
Molecular Structure. The unit cell consists of four sym-
metry-related zirconium complexes, Zr(2,4-C7H11)(C17NH24)
(C17NH24 ) [(i-Pr)NCHPhCH2CMedCHCMedCH2], C7H11
)
dimethylpentadienyl). This complex represents a case of a bent
(i.e., nonparallel olefinic ligands) M(dienyl)(diene)(L) com-
(48) Yasuda, H.; Tatsumi, K.; Nakamura, A. Acc. Chem. Res. 1985, 18, 120-
(50) Newbound, T. D.; Arif, A. M.; Wilson, D. R.; Rheingold, A. L.; Ernst, R.
D. J. Organomet. Chem. 1992, 435, 73-84.
(51) Waldman, T. E.; Rheingold, A. L.; Ernst, R. D. J. Organomet. Chem. 1995,
503, 29-33.
126.
(49) Tomaszewski, R.; Arif, A. M.; Ernst, R. D. J. Chem. Soc., Dalton Trans.
1999, 1883-1890.
9
J. AM. CHEM. SOC. VOL. 125, NO. 7, 2003 1941

A R T I C L E S
Pillet et al.
Figure 3. Residual density in (a) the phenyl ring, (b) the pentadienyl ligand, and (c) the Zr-N-C8 plane (S < 0.8 Å-1). Contours of 0.1 e Å-3, positive
as solid lines and negative as dashed lines.
for the terminal carbon atoms.52,53 The location of the zirconium
center below the diene plane is inconsistent, however, with an
η2-enediyl (5) contribution.54
ED), linking the two bonded atoms and characterized by the
topological properties at the corresponding bond critical point
(BCP, minimum of ED along the bond path).
The molecular graph (“union of the closures of the bond
paths”20) deduced from the topological analysis of the experi-
mental density with the NEWPROP program58 is shown in
Figure 4. As expected, bond paths and BCPs are associated with
all C-C, C-N, and C-H bonds. For the symmetric configu-
ration of a metal bonded to an aromatic ring, bond paths link
the metal center to each of the aromatic C atoms, as calculated
by Bytheway et al.26 for group 2 metallocenes (M ) Mg or
Ca), although Bader and Matta28 observed either three or four
bond paths (at RHF and DFT levels, respectively) linking Ti
with a cyclopentadienyl ligand in another complex. In the
present case, in addition to the strong Zr-N interaction, only
two Zr-C contacts exhibit a bond path, one for each of the
dimethylpentadienyl (to C3) and dimethylbutadiene (to C8)
moieties.
The intramolecular Zr‚‚‚H24 contact of 2.4604(6) Å may
represent an agostic interaction. The small Zr-N-C16 angle
(102.86(4)°), as compared to 130.4(4)° for the Ti-N-C angle
in a similar titanium complex,6 indicates a distortion of the
C15-N-C16 moiety. However, the 2.4604(6) Å distance is
longer than some other reported Zr‚‚‚H agostic bonds (2.14 Å
in (SiH2Cp2)ZrC3H7+, 2.20 Å in Cp2ZrCH3+ 32 involved in the
)
catalytic action of zirconocenes in the polymerization of
olefins,32,33 although longer distances have been observed, such
as 2.48 Å Zr(CH2SiMe3)4(dmpe).55 Furthermore, the N-C16
and C16-H24 bonds (the latter before extension to the neutron
value) are not significantly lengthened, contrary to what would
be expected on the basis of an agostic Zr‚‚‚H24 interaction.32,33
However, this may not be necessary for an agostic interaction,
given that H2 “σ complexes” are known in which the H-H
distance is similar to that in free H2.56 More criteria are therefore
needed and will be provided from the detailed analysis of the
ED.
As shown in Figure 2, the dimethylpentadienyl ligands of
two neighboring complexes stack in parallel with short C-C
distances between the two center-of-symmetry related dimeth-
ylpentadienyl ligands (Table 3). The contacts involve π-π and
(C-H)-π interactions,57 as confirmed by the following electron
density analysis.
The positive sign of the Laplacian of the ED at both the Zr-
C8 and the Zr-C3 BCPs is as observed generally for metal
ligand interactions.19 Although according to the AIM theory a
positive value of the Laplacian at the BCP characterizes a
closed-shell interaction, different concepts have been developed
2
in recent work. In addition to FBCP and ∇ FBCP , the local kinetic
and total energy densities at the BCPs, G(FBCP) and E(FBCP),
respectively, which can be derived from the electron density
using a functional proposed by Abramov,59 have been used in
a density-based characterization of metal-metal and metal-
ligand bonding,24 leading to a different classification of bond
types.
One bond path, following a straight line, links the outside
carbon atom C8 of the butadiene fragment to Zr. No direct
bonding to the interior carbon atoms C9 and C10 or to C11 is
evident from the molecular graph. A related enediyl bonding
scheme implying two bond paths has been found by Bader et
al.28 for Ti-butadiene interactions in a complex in which, as
in the current compound, the butadiene bonds do not show bond
length alternation.
Molecular Graph and Binding Modes. According to the
AIM theory, a direct interatomic interaction is unambiguously
indicated by the existence of a bond path (line of maximum of
(52) Yasuda, H.; Nakamura, A. Angew. Chem., Intl. Ed. Engl. 1987, 26, 723-
742.
(53) Erker, G.; Kru¨ger, C.; Mu¨ller, G. AdV. Organomet. Chem. 1985, 24, 1-39.
(54) Murakami, M.; Itami, K.; Ito, Y. Organometallics 1999, 18, 1326-1336.
(55) Cayias, J. Z.; Babaian, E. A.; Hrncir, D. C.; Bott, S. G.; Atwood, J. L. J.
Chem. Soc., Dalton Trans. 1986, 2743-2744.
(56) Van Der Sluys, L.; Eckert, J.; Eisenstein, O.; Hall, J. H.; Huffman, J. C.;
Jackson, S. A.; Koetzle, T. F.; Kubas, G. J.; Vergamini, P. J.; Caulton, K.
G. J. Am. Chem. Soc. 1990, 112, 4831-4841.
(57) Hunter, C. A.; Sanders, J. K. M. J. Am. Chem. Soc. 1990, 112, 5525-
5534.
(58) (a) Souhassou, M.; Blessing, R. H. J. Appl. Crystallogr. 1999, 32, 210-
217. (b) Souhassou, M. “Atomic properties from electron densities: program
Newprop-int”, ECM XIX, Nancy 2000, abstract S2-M2-P2.
(59) Abramov, Y. A. Acta Crystallogr., Sect. A 1997, 53, 264-272.
9
1942 J. AM. CHEM. SOC. VOL. 125, NO. 7, 2003

Interactions in an Organozirconium Complex
A R T I C L E S
Figure 4. Localization of the critical points of the electron density in (a) the Zr coordination sphere and (b) the interdimer region. Only relevant critical
points are depicted.
The ED at the BCP is lower for Zr-C3 (0.31 e Å-3) than
for Zr-C8 (0.42 e Å-3), in agreement with the asymmetry in
the coordination distances and therefore the strengths of the
interactions with the butadiene and pentadienyl groups. The
strongest interaction occurs with the nitrogen atom, the ED at
positive lobes correspond to an increase of the 4dz orbital
population with regards to the isolated zirconium atom (the
5s24d2 valence electronic state has been taken as reference),
whereas the negative lobes indicate a depopulation of the 4dxy
atomic orbital. The kidney shape of the positive lobes results
from the enediyl coordination mode, which elongates the
deformation density in the Zr-C8-C11 plane. The Zr 4d orbital
populations, derived from the multipolar expansion of the
deformation density,62 are listed in Table 5. Using only the 4d
monopole to derive the 4d atomic orbital populations leads to
an inconsistent negative population for the 4dxz orbital, likely
due to the impossibility of deconvoluting the 5s and 4d electrons
into two separate monopoles, as discussed above. We have
therefore adjusted the 4d orbital populations in Table 5 by
shifting 5s electrons equally into all d orbitals, such that the
population of the 4dyz orbital becomes equal to zero. Such an
adjustment is clearly appropriate, given the fact that the 4d
orbitals are substantially stabilized relative to the 5s orbital for
either Zr2+ or Zr4+. Table 5 shows good qualitative agreement
between models III and IV after the 5s electron transfer.
2
the Zr-N BCP being 0.88 e Å-3
.
The interactions in the present zirconium compound are
certainly more extensive than the binding suggested by the
experimental molecular graph. Given that complexes with
substantial enediyl character typically exhibit pronounced long-
short-long carbon-carbon bond patterns,2,52-54,60 the absence
of bond length alternation of the butadiene group suggests a
similar contribution of the three C-C bonds in the coordination
interactions, contrary to what the molecular graph indicates.
Theoretical evidence on metal carbonyl clusters shows that
bonding interactions can exist even in the absence of a bond
path.61 In addition, the Zr atom is positioned below the diene
and dienyl ligands, in contrast to expectations based on 5 and
6. For the dienyl coordination, the C3-Zr vector has rotated
70° from the expected location based on 6. A closer analysis
of the ED provides further insight into the nature of the bonding.
The characteristics of the deformation density and 4d orbital
populations can be understood in the context of the Dewar-
Chatt-Duncanson model,63,64 which has found support in
numerous charge density studies. Both delocalized ligands
2
donate π ED to the dz atomic orbital of zirconium through
σ-bonding (Figure 6b), which implies that the occupied frontier
molecular orbitals in this zirconium complex exhibit a high metal
2
4dz character. Similar π-donation interactions should involve
the 4dxz orbital, which has a relatively large population (Table
Electron Density around Zr and the 4d Atomic Orbital
Populations. The deformation of the valence ED of zirconium
is illustrated in Figure 5c,d, and a 3D representation is given in
Figure 6. Two kidney-shape lobes of positive deformation
density are directed toward the conjugated systems of both
ligands (maximum of 0.6 e Å-3), and four negative lobes
(minimum of -0.5 e Å-3) are located in the perpendicular plane.
The local coordinate system for Zr has been chosen according
to these directions, assuming that the z axis is along the positive
lobes and the x axis is pointing toward the nitrogen atom. The
5). More surprising are the low occupancy of the 4dxy orbital
2
2
and a significant occupancy of the 4dx -y orbital, contrary to
what is expected from usual crystal field arguments. In the XY
plane (Figure 5c), the lone pair of nitrogen is spread out and
2
2
directed toward Zr through σ-donation into the Zr 4dx -y atomic
orbital (Figure 6c), evidenced by its electron occupancy. In
addition to this N f Zr σ-donation, the nitrogen atom donates
π electron density to Zr by N(2p)-Zr(4dxz) orbital overlap,
(62) Holladay, A.; Leung, P.; Coppens, P. Acta Crystallogr., Sect. A 1983, 39,
377-387.
(63) Dewar, M. J. S. Bull. Soc. Chim. Fr. 1951, C71-C79.
(64) Chatt, J.; Duncanson, L. A. J. Chem. Soc. 1953, 2939-2947.
(60) Arif, A. M.; Ernst, R. D.; Melendez, E.; Rheingold, A. L.; Waldman, T. E.
Organometallics 1995, 14, 1761-1769.
(61) Macchi, P.; Sironi, A. Coord. Chem. ReV., in press.
9
J. AM. CHEM. SOC. VOL. 125, NO. 7, 2003 1943

A R T I C L E S
Pillet et al.
Figure 5. Static deformation density for model III in (a) the dimethylpentadienyl ligand, (b) the butadiene fragment, (c) the xy coordination plane of Zr, and
(d) the xz coordination plane of Zr. In part d, the N atom is out of the plane. Contours are as in Figure 3.
consistent with the above-noted occupancy of the 4dxz atomic
orbital (Figure 6d). It is possible that the low occupancy of the
4dxy orbital may derive from a δ back-bonding interaction, and,
in fact, pentadienyl ligands have been proposed to serve
generally as strong δ acids. The high formal metal oxidation
state in this case would seem to preclude much of this, although
it could be that such an interaction with the diene ligand
contributes to its enediyl character. This issue will need to be
addressed through additional studies.
The QTAIM provides a unique decomposition of the electron
density of the system in open subsystems (the atomic basins),
delimited by interatomic surfaces, defined according to the zero
flux condition in the gradient vector field of the electron density
as ∇bF‚bn ) 0. The atomic and fragment charges from numerical
integration over the atomic basins,65 derived using program
NEWPROP,58 are given in Table 6. The results indicate a charge
transfer of 2.16 e from the Zr atom to the ligands, more localized
on the C17NH24 ligand (1.48 e) than on dimethylpentadienyl
(0.68 e). The N atom has a considerable charge of -1.05 e,
indicating high electrostatic Zr-N interactions in addition to
the σ-π N f Zr donations discussed above. Bader et al.28 report
a high charge transfer of “approximately 3 e” from Ti to
cyclopentadienyl and diene fragments in a similar complex.
Electron Density Distribution of the Dimethylpentadienyl
Ligand. In addition to the BCPs located in each of the covalent
C-C and C-H bonds, an H‚‚‚H bond path formally closes the
open edge of the dimethylpentadienyl ligand. This feature is of
interest given the observation that metal pentadienyl complexes
can undergo loss of H2 under thermal conditions or during mass
spectroscopic studies, with conversion to cyclopentadienyl.66-68
A related bond path is not found for the diene ligand, which is
characterized by a longer open edge.
The static deformation density (total ED minus ED for
isolated atoms) in the plane of the dimethylpentadienyl ligand
is shown in Figure 5a. The features in the C1-C2, C2-C3,
C3-C4, and C4-C5 bonds are similar, as expected from
electronic conjugation effects. The ED and Laplacians at the
BCPs in the C-C bonds mirror the differences in bond lengths
(Table 7). The ellipticities of the C-C bonds of the dimethyl-
pentadienyl ligand show the same pattern. The ellipticity
averages 0.12 for the longer C4-C7 and C2-C6 bonds, 0.22
for C2-C3 and C3-C4, and 0.25 for the shorter C1-C2 and
C4-C5 bonds. The differences in bond lengths, ED at the BCP,
and ellipticity consistently reflect the distortion of the penta-
dienyl conjugated system as a result of the interactions with
(65) Pillet, S.; Souhassou, M.; Lecomte, C.; Rabu, P.; Massobrio, C.; Drillon,
M. Phys. ReV. B, submitted.
(66) Mann, B. E.; Manning, P. W.; Spencer, C. M. J. Organomet. Chem. 1986,
312, C64-C66.
(67) Kralik, M. S.; Rheingold, A. L.; Ernst, R. D. Organometalics 1987, 6,
2612-2614.
(68) Kirss, R. U.; Quazi, A.; Lake, C. H.; Churchill, M. R. Organometalics
1993, 12, 4145-4150.
9
1944 J. AM. CHEM. SOC. VOL. 125, NO. 7, 2003

Interactions in an Organozirconium Complex
A R T I C L E S
Figure 6. Three-dimensional representation of (a) the static deformation density around Zr atom for model III and schematic representation of the (b) Zr
r diene σ donation, (c) Zr r N σ donation, and (d) Zr r N π donation. Isocontour of 0.2 e Å-3 (positive in blue).
Table 5. 4d Orbital Populations for the Zr Atom (in e)
Table 7. Topological Properties of the Electron Density at the
BCPsa
2
2
2
d
z
model
d
d
xy
d
xz
d
yz
total
x -y
2
bond
d1
d2
d
F(brCP
)
∇ F(brCP
)
ꢀ
III (multipolar) 0.17(3) 0.43(3) -0.24(3) 0.40(3) -0.29(3) 0.47(7)
III (multipolar)a 0.46(3) 0.72(3)
IV (multipolar) 0.60(3) 0.77(3)
0.05(3) 0.69(3)
0.22(3) 0.76(3)
0.00(3) 1.92(7)
0.11(3) 2.46(7)
C11-C13
C11-C10
C10-C9
C9-C8
0.738
0.660
0.757
0.860
0.776
0.766
0.657
0.735
0.719
0.682
0.788
0.776
0.788
1.071
1.255
1.155
1.797
1.686
1.850
1.327
0.787
0.775
0.668
0.589
0.744
0.770
0.736
0.711
0.717
0.715
0.732
0.747
0.685
0.960
1.219
1.212
1.797
1.213
1.287
1.447
1.5239(9)
1.4347(8)
1.4248(9)
1.4479(9)
1.5199(9)
1.5366(9)
1.3918(9)
1.4454(9)
1.4344(9)
1.3971(9)
1.5195(9)
1.5217(9)
1.4710(8)
2.0309(5)
2.4714(6)
2.3535(6)
3.595(1)
1.48
1.89
1.75
1.67
1.60
1.57
2.01
1.93
1.85
2.16
1.51
1.60
1.77
0.86
0.31
0.42
0.03
0.04
0.02
0.03
-8.4
-14.1
-11.1
-6.8
-10.3
-9.6
-14.7
-14.0
-12.5
-18.4
-8.3
-9.95
-7.82
7.7
0.14
0.44
0.65
0.39
0.08
0.10
0.26
0.26
0.18
0.25
0.11
0.14
0.01
a After transferring 5s electrons to the 4d shell to eliminate the dxy
negative population (see text).
C9-C12
C11-C14
C1-C2
Table 6. Selected Atomic Charges from Numerical Integration
C2-C3
over the Atomic Basinsa
C3-C4
C4-C5
atom
charge
atom
charge
C2-C6
Zr
N
+2.16
-1.05
-0.46
-0.12
-0.44
-0.08
-0.26
-0.41
-0.46
C8
C9
-0.26
-0.23
-0.36
+0.00
-0.23
-0.35
+0.06
+0.13
-0.68
-1.48
C4-C7
N-C16
Zr-N
C1
C2
C3
C4
C5
C6
C7
C10
C11
C12
C13
H24
H
Zr-C3
3.5
4.2
0.3
0.5
0.3
0.4
Zr-C8
C3‚‚‚C3b
C1‚‚‚H10b
C5‚‚‚H7b
H10‚‚‚H7b
2.8077(6)
3.0629(6)
3.338(1)
C7H11 ligand
C17NH24 ligand
a d is the bond length (Å); d1 and d2 are the distances (Å) from the CP
a The total charge obtained on the asymmetric unit is +0.011 e, whereas
the integrated volume is 540.138 Å3, which represent global errors of 0.004
and 0.4% due to the integration procedure.
to each of the linked atoms, respectively. F(brCP) and ∇ F(brCP) are the electron
2
density (e Å-3) and Laplacian (e Å-5) of the electron density at the CP,
respectively. ꢀ is the dimensionless ellipticity of the bonds. b 2 - x, -y,
-z.
Zr, the double-bond character being more localized on C1-C2
and C4-C5 (cf. 2).
Figure 7 presents the deformation density in the planes
bisecting the C-C bonds of the conjugated system. The
ellipticity and therefore the π character of each are revealed by
the elongation of the deformation density in the direction roughly
perpendicular to the best plane. However, especially for the
C2-C3 bond, the principal axes of the ellipsoids deviate from
this direction by a tilt toward the Zr atom. The π-like molecular
orbitals are apparently not constructed from pure pz carbon
orbitals (z perpendicular to the plane of the conjugated system),
but they contain a significant contribution from the px and py
orbitals. This observation provides experimental substantiation
9
J. AM. CHEM. SOC. VOL. 125, NO. 7, 2003 1945

A R T I C L E S
Pillet et al.
Figure 7. Deformation density in the plane bisecting to the (a) C1-C2, (b) C2-C3, (c) C3-C4, (d) C4-C5, (e) C8-C9, (f) C9-C10, and (g) C10-C11
bonds. The horizontal arrow represents the direction perpendicular to the best planes (pentadiene and butadiene), whereas the diagonal arrow represents the
direction of the projection of Zr on the plane of the figure. Contours are as in Figure 3.
for the decades-old proposals, based upon observations of
substituent tilts out of a given ligand plane, that the p orbitals
of both cyclopentadienyl69,70 and pentadienyl ligands71 were in
effect tilting (more accurately, rehybridizing) to optimize overlap
with the more compact metal centers (e.g., 7).
orbitals is evident from the shape of the surface, as indicated
by the arrows in Figure 9.
As discussed previously, the zirconium complexes form
dimers in which the dimethylpentadienyl ligands of two
neighboring complexes stack parallel to each other. This
particular geometry results from π-π57 and (C-H)-π72
intermolecular interactions, as indicated by the presence of a
number of BCPs between the ligands (Figure 4b). As shown
by the low ED at the corresponding BCPs (0.02-0.04 e Å-3),
the intermolecular interactions represented by these bond paths
are nevertheless rather weak.
Electron Density Distribution of the Diene Fragment. The
high ellipticities of the C8-C9, C9-C10, and C10-C11 bonds
(0.39, 0.65, 0.44) mean that the corresponding ED is more
elongated in the direction almost perpendicular to the plane of
the conjugation (Figure 7). As for two of the bonds of the
pentadienyl group, a tilt of the deformation density ellipsoids
of the C8-C9 and C10-C11 bonds toward the Zr direction is
observed. Therefore, even though an η1 binding mode is implied
by the molecular graph, the extended conjugated system interacts
with the Zr atom. Because of the bending of the butadiene and
pentadienyl fragments and the resulting differences in Zr-C
bond lengths, the local distribution of BCP, RCP, and CCPs is
also far less regular than that found for group 2 metallocenes.26
Thus, one again sees that the whole conjugated system of
the pentadienyl ligand appears affected by the proximity of the
transition metal atom.
Bader et al.28 and Bytheway et al.26 used the presence or
absence of VSCCs (valence shell charge concentrations corre-
sponding to maxima in the negative of the Laplacian) near the
C atoms to detect and characterize bonding with Ti and Mg,
respectively. A VSCC is located near C3 in the direction of Zr
(Figure 8), but it is absent on C1, C2, C4, and C5, in accordance
with the strong Zr-C3 interaction evident from the bond path
analysis.
A three-dimensional representation of the total ED, illustrating
the coordination of Zr by the pentadienyl group, is presented
in Figure 9. The largest overlap between the atomic EDs occurs
between Zr and C3. In addition, significant contacts between
Zr and all of the C-C bonds are revealed, even though no bond
paths are involved. The orientation of the π-like molecular
As in the pentadienyl ligand, the positions of the VSCC of
the carbon atoms of the butadiene group (Figure 8) give
evidence for localized Zr-C interactions, only C8 and C11
exhibiting VSCCs in the direction of the Zr atom, in accord
with substantial enediyl character (i.e., 4).
Potential Agostic Interactions. The short Zr‚‚‚H24 and Zr-
C16 distances (2.4604(6) and 2.7601(6) Å, respectively),
(69) Elian, M.; Chen, M. M. L.; Mingos, D. M. P.; Hoffmann, R. Inorg. Chem.
1976, 15, 1148-1155.
(70) Haaland, A. Acc. Chem. Res. 1979, 12, 415-422.
(71) Ernst, R. D. Struct. Bonding (Berlin) 1984, 57, 1-53.
(72) Nishio, M.; Hirota, M.; Umezawa, Y. The CH-π Interaction; Wiley-
VCH: New York, 1998.
9
1946 J. AM. CHEM. SOC. VOL. 125, NO. 7, 2003

Interactions in an Organozirconium Complex
A R T I C L E S
F
F
2
Figure 8. Contour map of the L ) -∇ F function in the (a) Zr-C9-C10, (b) Zr-C8-C11, and (c) Zr-C4-C3 planes. Isocontours of x‚10n e Å-5
(r)
(r)
with n ) 0, (1, 2 and x ) 0, (2, (4, (8, positive as red solid lines, negative as blue dashed lines. BCP and RCP are depicted as red and blue circles,
respectively. Bond paths are represented by lines.
Figure 9. Three-dimensional representation of the electron density in the
Zr-dimethylpentadienyl fragment. Isocontour of 0.2 e Å-3. Dashed arrows
show the contacts between Zr and the C1-C2 and C4-C5 bonds.
together with the small Zr-N-C16 angle of 102.86(4)°, suggest
that an agostic interaction exists in the zirconium complex.
Three-center (C-H)‚‚‚M interactions are quite common10,73-76
Figure 10. Gradient trajectories (black lines) and total electron density
and would provide an explanation for the small Zr-N-C16
angle. Such complexes have been proposed to be in a state of
arrested oxidative addition, leading to two general situations.10,11
The first involves an early metal center with a d0 configuration,
so that oxidative addition cannot occur, and only a σ donor
interaction from the C-H bond to the metal center exists. In
other complexes, the presence of d electrons on the metal center
allows for back-bonding into the C-H bond’s σ* orbital. In
such cases, a stronger overall interaction is expected. While the
present Zr complex appears to be an example of the former
type, for which back-bonding should be precluded, the situation
is more complicated in the specific case of â-agostic complexes.
In a â-agostic ethyl complex, for example, the agostic interaction
may still lead to transfer of the hydride to the d0 metal center.
In essence, as the formal C-H oxidative addition occurs, one
can regard the complex as also undergoing a simultaneous C-C
reductive elimination, converting the C-C bond to a CdC bond.
In fact, for the present zirconium complex, then, the possibility
of back-bonding to the C16-H24 bond does therefore exist,
although there would be a replacement of the highly favorable
Zr-N bonds (both σ and π) by the ensuing hydride and imine
coordinations. The presence of the favorable Zr-N bond would
therefore be expected to greatly inhibit the back-bonding
(red lines) for model III in the Zr-N-C16-H24 plane. Bond CPs are
depicted as red circles. Contour levels of 0.1 e Å-3 are used for the total
electron density. The gradient trajectories are computed in a slice and
projected on the plane of the figure, so that some of them appear to cross
each other.
component for the interaction. No BCP and bond path are found
connecting Zr‚‚‚H24 or Zr‚‚‚C16 (Figure 10). There also is no
apparent curvature in the Zr-N bond path, whereas at least in
â-agostic alkyl complexes, bent M-C bond paths have been
observed.34 Conceivably, however, the high Zr-N bond strength
might offset such a tendency. In a recent investigation of agostic
bonding in an alkyllithium complex, Scherer et al. analyze the
ellipticity of the CR-Si bond in the Li-CR-Siâ-Cγ-Hγ
backbone and conclude that delocalization rather than Li‚‚‚H-C
agostic interaction is responsible for the observed distortions
of the molecule.77 Such an explanation seems inapplicable to
the current complex, as evidenced by the absence of ellipticity
of the N-C16 bond. Finally, the atomic charge obtained by
numerical integration over the atomic basin for H24 is positive
(+0.05), as opposed to what had been observed by Popelier in
a calculation on the R-agostic CH3TiCl2 cation;78 this positive
charge would be consistent with a primarily σ (donation)
interaction.
As the ED results thus do not provide any indication for the
existence of an agostic bridge in the zirconium complex, other
(73) Crabtree, R. H.; Holt, E. M.; Lavin, M.; Morehouse, S. M. Inorg. Chem.
1985, 24, 1986-1992.
(74) Crabtree, R. H. Angew. Chem., Int. Ed. Engl. 1993, 32, 789-805.
(75) Brookhart, M.; Green, M. L. H. J. Organomet. Chem. 1983, 250, 395-
(77) Scherer, W.; Sirsch, P.; Shorokhov, D.; McGrady, G. S.; Mason, S. A.;
Gardiner M. G. Chem.-Eur. J. 2002, 8, 2324-2334.
(78) Popelier, P. L. A.; Logothetis, G. J. Organomet. Chem. 1998, 555, 101-
111.
408.
(76) Brookhart, M.; Green, M. L. H.; Wong, L.-L. Prog. Inorg. Chem. 1988,
36, 1-124.
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A R T I C L E S
Pillet et al.
physical evidence must be examined. There is first of all the
small Zr-N-C angle, leading to a bend of ca. 27° toward the
zirconium center, as compared to an analogous titanium
complex. While one might attempt to attribute this tilt to a steric
interaction, it does not seem reasonable that one species would
tilt some 27° without the opposing species also undergoing a
noticeable tilt, in the opposite direction. For complexes with a
potential (C-H)‚‚‚M interaction, Crabtree et al.73 have defined
the distance, dbp, from the given metal center to the C-H
bonding pair of electrons, and the effective covalent radius of
the C-H bonding electrons rbp, obtained by subtracting the metal
radius from dbp. From examination of these distances, they have
“found no cases in which rbp is less than 1.9 Å in an 18-electron
complex,” showing “that the C-H bond is not close to the metal
simply by accident but that the 2-electron deficiency is required
for bridging to occur.”73 In the present zirconium complex, dbp
is 2.51 Å, which, using a Zr radius of 1.60 Å, corresponds to
an rbp value of ∼0.9 Å. This is well below the 1.9 Å limit and
thus indicative of a metal-C-H interaction. The M-H-C
angle is calculated as 94.32(3)°, again in a typical range for
accepted agostic interactions.
and theoretical studies on a wide range complexes with agostic
and/or π interactions.
Concluding Remarks
This high-resolution synchrotron X-ray diffraction study has
allowed for the determination of an accurate crystal structure
for the title zirconium complex as well as a complete ED
analysis. We have shown that experimental determination of
ED distributions and subsequent topological analysis are feasible
even for second-row transition-metal-based organometallic
compounds by minimizing absorption effects and using high-
quality relativistic scattering factors.
The ED distribution and its topological analysis give new
insight into the electronic structure of the title zirconium
complex. Bond paths were observed between the zirconium
center and the nitrogen atom, the diene, and dienyl ligands. Not
surprisingly, the Zr-N interaction is strongest. Although only
one bond path each is found linking the zirconium center with
the diene/enediyl and dienyl ligands, electron density ellipticities
indicate that π orbitals on the carbon atoms of these ligands
interact with the metal center through polarization and hybrid-
ization effects, as also suggested by the spread-out lobes on
the metal center and the electron density ellipticities in some
of the unsaturated C-C bonds of the ligand. Comparing the
diene/enediyl and dienyl bonding, the diene’s C-C bonds have
lower EDs and less negative Laplacians at their BCPs, but higher
ellipticities than the dienyl C-C bonds, indicating stronger
interactions of the metal center with the diene fragment. This
is consistent with the diene’s dianionic character and generally
higher reactivity.81
The lack of an apparent reduction in the C-H coupling
constant appears to argue against a (C-H)‚‚‚Zr interaction.
However, the fact that the complex has a d0 configuration
(considering the diene ligand as an enediyl) would seem to
preclude any substantial back-bonding interaction, and this could
lead to a weak agostic interaction and hence a relatively high
C-H coupling constant. Indeed, a relatively high J(13C-H)
value has been observed in another formally d0 complex believed
to possess an agostic interaction.79,80
The 4d atomic orbitals of Zr, derived from the modeled ED,
exhibit unusual populations. The orbitals directed toward the
Thus, while the data at hand do not explicitly establish what
sort of interaction is responsible for the small Zr-N-C angle,
the overall situation is reminiscent of observations made by
Popelier78 on rotation of the methyl group in the CH3TiCl2
cation: “In going from the staggered to the eclipsed conforma-
tion, the C-H3 bond becomes longer, the Ti-C-H3 angle
reduces to almost 90°, the Fb value is reduced, and the electron
population of H3 increases. These effects are collectively
reminiscent of the formation of an agostic bond (potentially
between Ti and H3), although there is clearly no BCP present.
So although both geometrical effects and AIM properties point
in the direction of an R-agostic interaction, we do not find a
bond expressing this interaction.” A parallel situation was found
for the agostic Ti(C2H5)Cl3(dmpe) complex, wherein an ex-
tremely flat gradient path was observed, leading the authors to
the expectation that bond critical points may not always be
observed for agostic interactions.34 The current results, together
with the aforementioned observations, thus point to an interest-
ing and important dichotomy concerning metal complexes with
potential agostic interactions. It is clear that such a discrepancy
between the ED results and the observed geometric distortions
needs to be addressed in detail, for a proper understanding to
be obtained for the bonding in these important types of
complexes, and there is therefore a great need for further ED
2
2
2
ligands (4dz and 4dx -y ) are not depopulated as could be
expected from ligand field effects. The metal-ligand interactions
2
are driven by σ-donation from both π ligands to the 4dz orbital
2
2
of zirconium, by σ-donation from N to the 4dx -y orbital, and
by π-donation from N to the 4dxz orbital, in addition to a mean
charge transfer of 2.16 e from Zr to the organic ligands, as
derived by numerical integration of the ED over the topologi-
cally defined atomic basins.
Although the substantial distortion of the isopropyl group
toward the zirconium center appears to indicate the presence
of some sort of agostic interaction, the topological analysis of
the ED in the region does not reveal any obvious indication
that such an interaction exists. Thus, there is no bond path and
corresponding BCP, and both structural and spectroscopic data
also do not indicate obvious weakening of any bonds, which
may be associated with agostic interactions. The ED analysis
therefore does not provide an explanation for the small Zr-
N-C16 angle and the proximity of the C-H bond and the metal
atom. Additional studies will need to be undertaken to address
this issue.82
In summary, these studies have provided the first experimental
data concerning the electron density distribution in metal
complexes with three (diene, dienyl, and amide) important types
of ligands. They have revealed how the electron densities of
these ligands respond to the presence of a zirconium atom and
have thereby demonstrated that metal-ligand bonding interac-
(79) Thompson, M. E.; Baxter, S. M.; Bulls, A. R.; Burger, B. J.; Nolan, M.
C.; Santarsiero, B. D.; Schaefer, W. P.; Bercaw, J. E. J. Am. Chem. Soc.
1987, 109, 203-219.
(80) It would be possible for both C-H and C-N interactions to occur with
the Zr center, one serving to increase the C-H coupling constant and the
other decreasing it.
(81) Basta, R.; Kulsomphob, V.; Ernst, R. D., unpublished results.
(82) Harvey, B. G.; Rheingold, A. L.; Ernst, R. D., work in progress.
9
1948 J. AM. CHEM. SOC. VOL. 125, NO. 7, 2003

Interactions in an Organozirconium Complex
A R T I C L E S
tions may be present even in the absence of formal bond paths.
It can be expected that systematic ED studies of key types of
early through late organometallic compounds should lead to a
much deeper understanding of σ, π, and agostic interactions in
these compounds and to insight into key reactions such as
oxidative additions and polymerizations.
National Science Foundation. Research was carried out in part
at the National Synchrotron Light Source at Brookhaven
National Laboratory, which is supported by the U.S. Department
of Energy, Division of Materials Sciences and Division of
Chemical Sciences. We thank Professor Arnold L. Rheingold
for providing structural information on the title compound prior
to publication.
Acknowledgment. Support of this work by the National
Science Foundation (CHE9981864 and CHE9617268) and the
U.S. Department of Energy (DE-FG02-86ER45231) is gratefully
acknowledged. The Center for Computational Research at
SUNY/Buffalo is supported by a grant (DBI9871132) from the
Supporting Information Available: CIF file of the 16 K
crystal structure. This material is available free of charge via
the Internet at http://pubs.acs.org.
JA021133I
9
J. AM. CHEM. SOC. VOL. 125, NO. 7, 2003 1949