Neutral and anionic transition metal complexes supported by decafluorodiphenylamido ligands (see abstract)

Article abstract of DOI:10.1016/S0277-5387(02)01258-5

Reaction of MN(C₆F₅)₂ (M = Na, K) with transition metal halides results in the formation of transition metal complexes incorporating decafluorodiphenylamido ligands. TiCl₃(THF)₃ reacts with 3 equiv. NaN(C₆F₅)₂ to yield the 'metallate' complex {Na(THF)₂}{Ti[N(C₆F₅)₂] ₄} (1). Single crystal X-ray diffraction studies reveal a tetrahedral titanium center complexed by four decafluorodiphenylamido ligands; while two THF ligands and four fluorine atoms coordinate the sodium cation. ZrCl₄ reacts with 3 equiv. KN(C₆F₅)₂ to give {K(η⁶-C₇H₈)₂} {ZrCl₂[N(C₆F₅)₂]₃} (2). The ¹⁹F NMR spectrum of 2 reveals phenyl resonances in a 2:1 ratio, consistent with a trigonal bipyramidal structure being maintained in solution. The crystal structure of 2 reveals a pseudooctahedral structure, with the sixth-coordination site being completed by a weak Zr-F interaction with a pentafluorophenyl group of an amido ligand. The potassium counterion interacts in an η⁶ fashion with two toluene rings in addition to a fluorine atom arising from one of the pentafluorophenyl groups. The reaction of VCl₃ with 3 equiv. KN(C₆F₅)₂ generates the 'metallate' complex K{VCl[N(C₆F₅)₂]₃} (3); the solid state structure of 3 reveals a distorted trigonal bipyramid with the coordination sphere being completed by a weak V-F interaction with the ortho-fluorine of one of the fluorophenyl amido ligands. Exposure of FeCl₃ to 3 equiv. KN(C₆F₅)₂ results in reduction of the metal center and the formation of the Fe(II) species Fe[N(C₆F₅)₂]₂(THF)₂ (4). Compound 4 is tetrahedral in the solid state with none of the weak M-F contacts observed for 1, 2, 3 and 5. CoI₂ reacts with 2 equiv. NaN(C₆F₅)₂ in the presence of pyridine to produce the expected product Co[N(C₆F₅)₂]₂(py)₂ (5); X-ray crystallography reveals a five-coordinate species in the solid state which is additionally stabilized by a weak Co-F interaction.

Full text of DOI:10.1016/S0277-5387(02)01258-5

Polyhedron 22 (2003) 153Á163
/
www.elsevier.com/locate/poly
Neutral and anionic transition metal complexes supported by
decafluorodiphenylamido ligands: X-ray crystal structures of
{Na(THF)2}{Ti[N(C6F5)2]4}, {K(h6-C6H5Me)2}{ZrCl2[N(C6F5)2]3},
K{VCl[N(C6F5)2]3}, Fe[N(C6F5)2]2(THF)2 and Co[N(C6F5)2]2(py)2
Garth R. Giesbrecht a, John C. Gordon b,ꢀ, David L. Clark a,ꢀ, Cybele A. Hijar b,
Brian L. Scott b, John G. Watkin b,ꢀ
a Nuclear Materials Technology (NMT) Division and Glenn T. Seaborg Institute for Transactinium Science, Los Alamos National Laboratory, Los
Alamos, NM 87545, USA
b Chemistry (C) Division, Los Alamos National Laboratory, Los Alamos, NM 87545, USA
Received 23 July 2002; accepted 1 October 2002
Abstract
Reaction of MN(C6F5)2 (MꢁNa, K) with transition metal halides results in the formation of transition metal complexes
/
incorporating decafluorodiphenylamido ligands. TiCl3(THF)3 reacts with 3 equiv. NaN(C6F5)2 to yield the ‘metallate’ complex
{Na(THF)2}{Ti[N(C6F5)2]4} (1). Single crystal X-ray diffraction studies reveal a tetrahedral titanium center complexed by four
decafluorodiphenylamido ligands; while two THF ligands and four fluorine atoms coordinate the sodium cation. ZrCl4 reacts with 3
equiv. KN(C6F5)2 to give {K(h6-C7H8)2}{ZrCl2[N(C6F5)2]3} (2). The 19F NMR spectrum of 2 reveals phenyl resonances in a 2:1
ratio, consistent with a trigonal bipyramidal structure being maintained in solution. The crystal structure of 2 reveals a pseudo-
octahedral structure, with the sixth-coordination site being completed by a weak Zrꢀ
/
F interaction with a pentafluorophenyl group
of an amido ligand. The potassium counterion interacts in an h6 fashion with two toluene rings in addition to a fluorine atom arising
from one of the pentafluorophenyl groups. The reaction of VCl3 with 3 equiv. KN(C6F5)2 generates the ‘metallate’ complex
K{VCl[N(C6F5)2]3} (3); the solid state structure of 3 reveals a distorted trigonal bipyramid with the coordination sphere being
completed by a weak VÁ
equiv. KN(C6F5)2 results in reduction of the metal center and the formation of the Fe(II) species Fe[N(C6F5)2]2(THF)2 (4).
Compound 4 is tetrahedral in the solid state with none of the weak MꢀF contacts observed for 1, 2, 3 and 5. CoI2 reacts with 2
equiv. NaN(C6F5)2 in the presence of pyridine to produce the expected product Co[N(C6F5)2]2(py)2 (5); X-ray crystallography
F interaction.
/
F interaction with the ortho-fluorine of one of the fluorophenyl amido ligands. Exposure of FeCl3 to 3
/
reveals a five-coordinate species in the solid state which is additionally stabilized by a weak Coꢀ
/
# 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Decafluorodiphenylamido; Titanium; Zirconium; Vanadium; Iron; Cobalt
1. Introduction
electronic and steric changes may be incorporated into
the ligand framework [1Á4]. The chemistry of transition-
metal amido complexes has been greatly accelerated by
the observation of catalytic activity [5Á11] and small
molecule activation [12,13]. Although a number of
studies have utilized pentafluorophenyl groups attached
/
The chemistry of transition metals coordinated by
amido ligands has grown dramatically in the past
decade, due in part to the realization that the amido
ligand may be an attractive alternative to the cyclopen-
tadienyl ligand as a result of the ease with which
/
to the nitrogen atom of amido ligands, [14Á
have been no reports to date of the use of the
decafluorodiphenylamido group, N(C6F5)2, as an
/21] there
ꢀ
/
ꢀ Corresponding authors. Tel.: ꢂ
7895
E-mail address: dlclark@lanl.gov (D.L. Clark).
/
1-505-665-6690; fax: ꢂ1-505-665-
/
ancillary ligand in transition metal complexes. We
were interested in the decafluorodiphenylamido ligand
0277-5387/02/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 2 7 7 - 5 3 8 7 ( 0 2 ) 0 1 2 5 8 - 5

154
G.R. Giesbrecht et al. / Polyhedron 22 (2003) 153Á163
/
due to its facile synthesis [22], its high solubility in
hydrocarbon solvents, and its suitable steric require-
ments. The electron withdrawing nature of this ligand
may be understood by considering the pKa of the amine,
which has been determined to be very similar to those of
trifluoroacetic acid and pentafluorobenzoic acid [23].
Studies of pKa values of a range of amines in various
solvents revealed that the pKa of aniline in DMSO is
30.6, diphenylamine is 25.0 and decafluorodiphenyla-
mine is 11.5 [24]. This suggested that the decafluorodi-
phenylamido ligand may be helpful in stabilizing highly
electrophilic metal amido complexes as potential cata-
lysts for olefin polymerization [25]. Recently, we re-
ported the use of this ligand in organolanthanide
chemistry, which resulted in the isolation of the unusual
toluene complex, (h6-C7H8)Nd[N(C6F5)2]3 [26]. Here we
report the synthesis and crystallographic characteriza-
tion of transition metal centers supported by the highly
THF only; no resonances were observed in the 19F
NMR spectrum of 1, consistent with the paramagnetism
of a d1 Ti(III) metal center. In contrast, the reaction of
TiCl3(THF)3 with the unfluorinated analogue LiNPh2
yields the Ti(IV) product [Ti(NPh2)4], in which the
titanium center has been oxidized [27]. To the best of
our knowledge, no examples of tri-coordinate Ti(III)
complexes supported by diphenylamido ligands have
been reported.
The reaction of KN(C6F5)2 (3 equiv.) with ZrCl4 or
VCl3 yielded the tris amido products {K(C7H8)2}-
{ZrCl2[N(C6F5)2]3} (2) and K{VCl[N(C6F5)2]3} (3),
both of which additionally coordinated an equivalent
of KCl. {K(C7H8)2}{ZrCl2[N(C6F5)2]3} (2) was pro-
duced as a colorless, diamagnetic solid in moderate
yield. The reaction of ZrCl4 with various equivalents of
KN(C6F5)2 all generated the same product, indicating
that 2 is the preferred reaction product. This is in
contrast to the reaction of KNPh2(dioxane)3 with
ZrCl4(THF)2, which produces the tetrakis-amido com-
plex Zr(NPh2)4(dioxane) regardless of the stoichiometry
employed [28]. The 19F NMR spectrum of 2 was
consistent with a trigonal bipyramidal structure being
maintained in solution (see later), with two sets of
pentafluorophenyl resonances observed in a 2:1 ratio.
Based on steric considerations, this is suggestive that
two of the decafluorodiphenylamido ligands reside in
the equatorial positions, with the remaining ligand
occupying an axial position. The 1H NMR spectrum
(C6D6) of 2 exhibited resonances attributable to free
toluene only, suggesting that the {K(h6-C7H8)2ꢂ} unit
observed in the solid-state structure may not be main-
tained in solution (see later), or that the arene unit has
exchanged with the NMR solvent. The presence of only
two distinct types of phenyl resonances in the 19F NMR
electron-withdrawing ꢀ/N(C6F5)2 ligand.
2. Results and discussion
2.1. Synthesis
The reaction of either NaN(C6F5)2 or KN(C6F5)2,
generated in situ by the reaction of NaH or KH with
HN(C6F5)2 in THF, with transition metal chlorides
resulted in the formation of new transition metal
complexes containing decafluorodiphenylamido ligands
(Eqs. (1)Á(5)).
/
3NaN(C6F5)2 ꢂTiCl3(THF)3
THF=tol
fNa(THF)2gfTi[N(C6F5)2]4g
(1)
RT; 18
h
1
spectrum of 2 also suggests that the metalÁfluorine
/
3KN(C6F5)2 ꢂZrCl4
THF=tol
interactions observed in the crystal structures of 2, 3 and
5 are weak and do not give rise to any additional
anisotropy in solution.
fK(C7H8)2gfZrCl2[N(C6F5)2]3g
THF=tol
(2)
(3)
(4)
RT; 18
h
2
3KN(C6F5)2 ꢂVCl3
3KN(C6F5)2 ꢂFeCl3
2NaN(C6F5)2 ꢂCoI2
KfVCl[N(C6F5)2]3g
The formation of the vanadium ‘metallate’ species
also contrasts with that reported for the unfluorinated
analogue, for which syntheses of V(NPh2)3(THF) [29]
V(NPh2)3(THF)(dioxane)0.5 [30] and V(NPh2)3 [31] have
been reported from the reaction of VCl3(THF)3 with 3
equiv. of the unsubstituted salt NaNPh2. The mechan-
ism of the reaction of VCl3 with KNPh2 has been shown
to involve the intermediate formation of K[V(NPh2)4]
[32] showing that the ‘metallate’ species are also
RT; 18
THF=tol
h
3
Fe[N(C6F5)2]2(THF)2
4
RT; 18
h
THF=tol=pyridine
Co[N(C6F5)2]2(py)2 (5)
5
RT; 18
h
In the case of titanium, zirconium and vanadium,
various equivalents of amido ligand were incorporated,
and the products included sodium or potassium centers,
giving anionic or ‘metallate’ species. The reaction of
NaN(C6F5)2 (3 equiv.) with TiCl3(THF)3 gave the blue/
green Ti(III) product, {Na(THF)2}{Ti[N(C6F5)2]4} (1)
in low yield, in which each titanium center was bound to
four amido ligands. The titanium atom remained in the
accessible with the less electron withdrawing ꢀ
/NPh2
ligand. K{VCl[N(C6F5)2]3} (3) was produced as a dark
red solid in low yield. FeCl3 reacted with 3 equiv. of
KN(C6F5)2 to produce the purple/brown Fe(II) species
Fe[N(C6F5)2]2(THF)2 (4) in moderate yield, in which
only two decafluorodiphenylamido ligands were evi-
dent. By comparison, the reaction of FeCl3 with 3 equiv.
of KNPh2(dioxane)3 in THF produces the metallate
ꢂ3 oxidation state, with the charge being balanced by a
/
{Na(THF)2ꢂ} counterion. The H NMR spectrum of
crystalline material exhibited broad peaks due to free
1

G.R. Giesbrecht et al. / Polyhedron 22 (2003) 153Á
/163
155
species K[Fe(NPh2)4], [33] in which the metal center has
not undergone reduction. Similarly, the reaction of
FeBr2 with stoichiometric amounts of MNPh2(dioxa-
Table 1
˚
Selected bond distances (A) and angles (8) for {Na(THF)2}-
{Ti[N(C6F5)2]4} (1)
ne)x (Mꢁ
/
Li, xꢁ
/
0; Mꢁ
/
K, xꢁ3) yields the expected
/
Bond lengths
disubstituted Fe(II) products [Fe(NPh2)2]2 [34] and
1
Fe(NPh2)2(dioxane)2 [34]. The H NMR spectrum of 4
Ti(1)ꢀN(1)
Na(1)ꢀF(11)
Na(1)ꢀO(1)
2.039(3)
2.477(3)
2.246(4)
Ti(1)ꢀN(2)
Na(1)ꢀF(16)
Ti(1)ꢀF(1)
2.039(3)
2.407(3)
3.094(3)
exhibited resonances for free THF only; no resonances
were observed in the 19F NMR spectrum, consistent
with the presence of a paramagnetic of Fe(II) center.
The reaction of NaN(C6F5)2 (2 equiv.) with CoI2
Bond angles
N(1)ꢀTi(1)ꢀN(1ꢀ)
N(1)ꢀTi(1)ꢀN(2ꢀ)
O(1)ꢀNa(1)ꢀO(1ꢀ)
O(1)ꢀNa(1)ꢀF(16)
O(1)ꢀNa(1)ꢀF(16ꢀ)
F(11)ꢀNa(1)ꢀF(16)
123.81(19) N(1)ꢀTi(1)ꢀN(2)
92.63(13) N(2)ꢀTi(1)ꢀN(2ꢀ)
117.21(13)
115.41(19)
128.53(12)
82.87(12)
96.1(3)
O(1)ꢀNa(1)ꢀF(11)
followed by recrystallisation from tolueneÁpyridine
/
151.27(12) O(1)ꢀNa(1)ꢀF(11ꢀ)
95.78(13) F(11)ꢀNa(1)ꢀF(11ꢀ) 136.20(16)
78.92(10) F(11ꢀ)ꢀNa(1)ꢀF(16) 69.31(9)
yielded the expected product, Co[N(C6F5)2]2(py)2 (5) in
moderate yield as dark red crystals. Although CoCl2
reacts with 2 equiv. of the unsubstituted salt LiNPh2 to
produce a mixture of [Li(THF)4][Co(NPh2)3] and
[Co(NPh2)2]2 [35] use of the larger halide CoBr2 gives
Co(NPh2)2(dioxane)2 when reacted with KNPh2(diox-
ane)3 in THF [36]. As observed for the titanium complex
1 and the iron species 4, the paramagnetism of
Co[N(C6F5)2]2(py)2 (5) rendered the 19F NMR spectrum
uninformative, while only resonances for free solvent
F(16)ꢀNa(1)ꢀF(16ꢀ) 86.03(14) Na(1)ꢀF(11)ꢀC(14) 145.1(2)
Na(1)ꢀF(16)ꢀC(20) 124.5(2)
interactions [41]. The closest approach of a fluorine
˚
atom to the titanium metal center is 3.094 A in the case
of F(1). The Naꢀ
unremarkable. Coordination of the sodium cation into
the ‘pocket’ formed by F(11), F(16), F(11ꢀ) and F(16ꢀ)
seems to have little effect on the conformation of the
two decafluorodiphenylamido ligands involved in this
bonding (i.e. those containing N(2) and N(2ꢀ)). In fact,
an essentially identical, although vacant, ‘pocket’ exists
at the opposite face of the molecule, formed by F(1),
˚
O distance of 2.246(4) A is also
/
1
were evident by H NMR spectroscopy.
2.2. Crystallographic studies
The above mentioned transition metal complexes 1Á
were further investigated by X-ray crystallography in
order to establish the nature of the metalÁligand
/
5
F(6), F(1ꢀ) and F(6ꢀ). The similarity between the N(2)ꢀ
/
/
Ti(1)ꢀN(2ꢀ) angle (115.41(19)8) and the N(1)ꢀTi(1)ꢀ
/
/
/
interactions present.
N(1ꢀ) angle (123.81(19)8) also indicates that coordina-
tion of the sodium cation does not dramatically affect
the spatial orientation of the fluorinated ligands. The
dihedral angle between the two aromatic rings on each
decafluorodiphenylamido ligand is close to 908, while
some of the aromatic rings on adjacent ligands are
2.2.1. {Na(THF)2}{Ti[N(C6F5)2]4} (1)
Single crystals of 1 that were suitable for an X-ray
diffraction study were grown by cooling a concentrated
toluene solution to ꢃ35 8C. Selected bond lengths and
/
angles are presented in Table 1. A thermal ellipsoid plot
giving the atom-numbering scheme used in the tables is
shown in Fig. 1; complete details of the structural
almost coplanar (e.g. the C(1)ꢀ
within 18 with the C(19ꢀ)ꢀC(24ꢀ) ring). Within the
extended lattice structure, one can observe two distinct
alternating layers-one ‘ionic’ layer which contains only
the titanium, sodium and oxygen atoms, and a ‘covalent’
layer containing only fluorine and carbon atoms.
/
C(6) ring is coplanar to
/
analyses of compounds 1Á5 are listed in Table 6.
/
Compound 1 co-crystallizes with a molecule of toluene
in the unit cell. The titanium metal center is coordinated
in pseudo-tetrahedral fashion by four decafluorodiphe-
nylamido ligands, while the sodium cation is bound to
two THF ligands and completes its coordination sphere
2.2.2. {K(C7H8)2}{ZrCl2[N(C6F5)2]3} (2)
Single crystals of 2 were grown from a concentrated
toluene solution at ꢃ35 8C; selected bond lengths and
by making short Naꢀ
atoms from four different pentafluorophenyl moieties.
The two independent TiꢀN bond lengths are identical at
2.039(3) A, which may be compared with the average
/
F interactions with four fluorine
/
/
angles are presented in Table 2. A thermal ellipsoid plot
giving the atom-numbering scheme used in the tables is
shown in Fig. 2. The complex crystallizes with one
molecule of toluene in the unit cell. The zirconium metal
center is coordinated in pseudo-octahedral fashion by
two cis chloride ligands, three nitrogen atoms from the
decafluorodiphenylamido ligands that define a fac
geometry, and a short ZrÁ Á ÁF interaction that lies trans
to one of the nitrogen atoms. The potassium cation
makes one KÁ Á ÁF interaction with a fluorine atom from
one pentafluorophenyl moiety, and an extended struc-
˚
˚
distances of 2.089(3) A seen in the Ti(III) complex Ti[(2-
˚
2.041(7) A in
[Na(12-crown-4)2][{(Me3Si)2N}2TiOC(CH2)SiMe2N-
(Me3SiN)-4-Me-C5H3N]3, [37] 2.035(7)Á
/
SiMe3], [38] 2.007(7)Á2.042(7) in [Li(12-crown-4){(Me3-
/
Si)2N}2TiCH2SiMe2NSiMe3], [39] and 2.027(8) and
˚
2.036(8) A in {Li(TMEDA)2}{Ti[N(SiMe3)2]2-
(CH2Ph)2} [40]. The Naꢀ
/
F distances of 2.407(3) and
2.477(3) A are entirely in line with those observed
previously in many examples of alkali-metalÁfluorine
˚
/

156
G.R. Giesbrecht et al. / Polyhedron 22 (2003) 153Á163
/
Fig. 1. A thermal ellipsoid view of {Na(THF)2}{Ti[N(C6F5)2]4} (1) drawn with 30% probability ellipsoids, and giving the atom number scheme used
in the tables. The interstitial toluene molecule is omitted for clarity.
tion sphere of potassium. The preference of the potas-
sium cation to interact with two arene rings in a multi-
hapto fashion, despite the fact that the preparative
reactions were carried out in a donor solvent (THF) is
noteworthy, but not unexpected. The attractive electro-
static interactions of alkali cation-p complexes has been
a topic of much recent synthetic and theoretical study
Table 2
˚
Selected bond distances (A) and angles (8) for {K(C7H8)2}-
{ZrCl2[N(C6F5)2]3} (2)
Bond lengths
Zr(1)ꢀN(1)
Zr(1)ꢀN(3)
Zr(1)ꢀCl(2)
K(1)ꢀꢀCl(1)
K(1)ꢀF(8)
K(1)ꢀC(38)
K(1)ꢀC(40)
K(1)ꢀC(42)
K(1)ꢀC(45)
K(1)ꢀC(47)
K(1)ꢀC(49)
2.102(2)
2.156(2)
2.4468(8)
Zr(1)ꢀN(2)
Zr(1)ꢀCl(1)
Zr(1)ꢀF(26)
2.179(2)
2.4882(8)
2.602(2)
3.0953(12)
3.247(4)
3.348(5)
3.160(4)
3.203(4)
3.345(6)
3.439(5)
3.0946(11) K(1)ꢀꢀCl(2)
[42Á
The largest deviations of the angles around zirconium
from octahedral geometry are the rather obtuse N(1)ꢀ
Zr(1)ꢀN(3) and N(1)ꢀZr(1)ꢀN(2) angles of 110.55(9)8
and 108.64(9)8, respectively, and the relatively acute
N(3)ꢀZr(1)ꢀF(26) angle of 68.04(7)8. ZrꢀN distances
are of two types; a relatively short Zr(1)ꢀN(1) distance
of 2.102(2) A and significantly longer Zr(1)ꢀN(2) and
Zr(1)ꢀN(3) distances of 2.156(2) and 2.179(2) A. We
note that the short ZrꢀN bond length occurs in the site
that is trans to the weak ZrÁ Á ÁF interaction, and
N(1)
/47].
2.892(2)
3.343(4)
3.258(5)
3.154(4)
3.224(4)
3.453(6)
3.313(4)
K(1)ꢀC(37)
K(1)ꢀC(39)
K(1)ꢀC(41)
K(1)ꢀC(44)
K(1)ꢀC(46)
K(1)ꢀC(48)
/
/
/
/
/
/
/
/
Bond angles
˚
/
N(1)ꢀZr(1)ꢀN(2)
N(2)ꢀZr(1)ꢀN(3)
N(2)ꢀZr(1)ꢀCl(1)
N(1)ꢀZr(1)ꢀCl(2)
N(3)ꢀZr(1)ꢀCl(2)
N(1)ꢀZr(1)ꢀF(26)
N(3)ꢀZr(1)ꢀF(26)
Cl(1)ꢀZr(1)ꢀF(26)
Zr(1)ꢀF(26)ꢀC(32)
108.64(9)
86.18(9)
89.66(6)
101.38(7)
147.44(6)
171.32(8)
68.04(7)
79.75(5)
107.10(15)
N(1)ꢀZr(1)ꢀN(3)
N(1)ꢀZr(1)ꢀCl(1)
N(3)ꢀZr(1)ꢀCl(1)
N(2)ꢀZr(1)ꢀCl(2)
Cl(1)ꢀZr(1)ꢀCl(2)
N(2)ꢀZr(1)ꢀF(26)
Cl(2)ꢀZr(1)ꢀF(26)
K(1)ꢀF(8)ꢀC(10)
110.55(9)
91.66(7)
86.88(6)
159.70(7)
85.99(3)
79.96(8)
79.42(4)
136.9(2)
˚
/
/
therefore, suggest that the shortness of the Zr(1)ꢀ
/
bond is due to the virtual absence of a trans-influence,
when compared with the other two amido ligands which
are both trans to chloride ligands. The two Zrꢀ
/
Cl bond
˚
lengths are very similar, at 2.4468(8) and 2.4882(8) A,
˚
F(26) interaction is 2.6021(17) A. Only
while the Zr(1)ꢀ
/
a few other examples of ZrÁ Á ÁF interactions are reported
in the literature, mainly for weakly coordinating fluori-
nated anions interacting with cationic zirconium metal
centers. For example, Marks et al. noted ZrÁ Á ÁF contacts
ture is then formed by means of KÁ Á ÁCl interactions
between the potassium and two zirconium-bound chlo-
ride ligands from the adjacent anion in the lattice. Two
h6-toluene solvent molecules also occupy the coordina-

G.R. Giesbrecht et al. / Polyhedron 22 (2003) 153Á
/163
157
Fig. 2. A thermal ellipsoid view of {K(C7H8)2}{ZrCl2[N(C6F5)2]3} (2) drawn with 30% probability ellipsoids, and giving the atom number scheme
used in the tables. The interstitial toluene molecule is omitted for clarity.
˚
of 2.416(3) and 2.534(3)
[HB(C6F5)3] [48,49] while Gade and co-workers have
A
in [(h-C5Me5)2ZrH]-
shown in Fig. 3. Compound 3 co-crystallizes with one
molecule of toluene per unit cell. The overall molecular
geometry consists of a vanadium metal center coordi-
nated in a distorted trigonal bipyramidal fashion by an
˚
reported ZrÁ Á ÁF distances of 2.535(5)
A
[50]
in [(2-
and
FC6H4NSiMe2)3CH]Zr(m-Cl)2Li(OEt)2
˚
A
2.563(8)
in HC[SiMe2N(2-FC6H4)]3Zr(S2C)Fe-
axial chloride ligand, an axial VÁ Á ÁFꢀ
/
C interaction with
(CO)2(h-C5H5) [51]. Also Erker has observed ZrÁ Á ÁF
the ortho-fluorine of one of the amido ligands, and three
decafluorodiphenylamido ligands which occupy meri-
dianal positions. The chain structure of this complex,
formed by means of KÁ Á ÁClÁ Á ÁKÁ Á ÁCl bridges is remi-
niscent of that seen in {Th[Me3SiCHC(But)NSi-
˚
distances of 2.408(2) A in (h-C5H4Me)2Zr[H2CCHCH-
˚
CH2B(C6F5)3] [52] and 2.4020(13) A in (h-C5H5)2Zr-
[H2CC(Me)CHCH2B(C6F5)3] [52] and a ZrÁ Á ÁF distance
˚
as short as 2.237(4) A has been documented in {(h-
C5Me5)[h-C5Me4CH2B(C6F5)3]ZrH} [53]. The Zrꢀ
/Cl
Me3)]2(m3-Cl)(m-Cl)2K(OEt2)}n [59]. The Nꢀ
angles within the equatorial plane are all roughly 1208,
while the axial Cl(1)ꢀV(1)ꢀF(12) angle measures
172.85(6)8. The vanadiumÁnitrogen distances of
/
Vꢀ/N
˚
distances are comparable to those of 2.475(3) A seen
in {C6H5C[N(SiMe3)][(N(myrtanyl)}3ZrCl and
2.4231(11) A in ZrCl{N[CH2CH2N(SiMe2Bu )]3} [54].
/
/
t
˚
/
˚
Cl distances of 3.0953(12) and 3.0946(11) A are
Kꢀ
/
˚
1.944(3), 1.991(3) and 2.000(3) A span the range of
slightly shorter than those observed in crystalline KCl
˚
(3.138 A) [55] while the K(1)ꢀ
/
F(8) distance of 2.892(2)
Table 3
˚
A is typical for interactions of this type [41]. Kꢀ
/C
˚
Selected bond distances (A) and angles (8) for K{VCl[N(C6F5)2]3} (3)
distances for the h6-bound toluene molecules lie in the
˚
range 3.154(4)Á
/
3.453(6) A, which may be compared
Bond lengths
with those found in [Lu{CH(SiMe3)2}3(m-Cl)K(h6-tolu-
V(1)ꢀN(1)
V(1)ꢀN(3)
V(1)ꢀF(12)
K(1)ꢀF(30)
K(1)ꢀCl(1)
1.991(3)
2.000(3)
2.284(2)
2.739(3)
3.0925(14)
V(1)ꢀN(2)
V(1)ꢀCl(1)
K(1)ꢀF(2)
K(1)ꢀF(32)
1.944(3)
2.2999(12)
2.727(3)
2.873(3)
˚
3.56 A) [56] [(Tmp)6Sm2(KCl)2(toluene)3]n
ene)2] (3.21Á
/
˚
(Tmpꢁ
/
2,3,4,5-tetramethylphospholyl; 3.21Á3.56 A)
/
[57] and [{(ButO)2Sb3(m-NCy)3(m3-NCy)}K(h6-toluene)]
˚
3.47 A) [58].
(3.20Á
/
Bond angles
N(1)ꢀV(1)ꢀN(2)
N(1)ꢀV(1)ꢀCl(1)
N(2)ꢀV(1)ꢀN(3)
N(2)ꢀV(1)ꢀF(12)
N(3)ꢀV(1)ꢀF(12)
V(1)ꢀF(12)ꢀC(12)
114.63(13) N(1)ꢀV(1)ꢀN(3)
97.56(10) N(1)ꢀV(1)ꢀF(12)
130.01(13) N(2)ꢀV(1)ꢀCl(1)
86.82(10) N(3)ꢀV(1)ꢀCl(1)
85.80(10) Cl(1)ꢀV(1)ꢀF(12)
109.3(2)
111.53(13)
76.83(10)
99.64(9)
2.2.3. K{VCl[N(C6F5)2]3} (3)
Cooling a concentrated 3:1 tolueneÁ
to ꢃ35 8C grew single crystals of 3 that were suitable for
X-ray diffraction. A list of relevant bond lengths and
angles is presented in Table 3; a thermal ellipsoid view is
/
hexane solution
92.27(9)
172.85(6)
/

158
G.R. Giesbrecht et al. / Polyhedron 22 (2003) 153Á163
/
approximately tetrahedral fashion by two nitrogen
atoms from decafluorodiphenylamido ligands and two
oxygen atoms from the THF ligands. The angles
subtended by iron range from 99.44(7)8 (N(1)ꢀ
O(1ꢀ)) to 132.40(9)8 (O(1)ꢀFe(1)ꢀO(1ꢀ)). The Feꢀ
distance of 2.0495(19) A is somewhat long for an
/
Fe(1)ꢀ
/
/
/
/
N
˚
˚
iron(II)-amido system; distances of Â1.91 A have
/
been reported for {Fe[N(SiMe3)2][m-O-2,4,6-tBu3-
C6H2]}2, [68] Fe[N(SiMePh2)2]2 [69] and [Fe(m-
NPh2)(NPh2)]2 [34]. A Feꢀ
/
N bond distance of 1.84(2)
A is found in Fe[N(SiMe3)2]2 [70]. The FeꢀO bond
length of 2.1193(16) A may be compared with the
˚
/
˚
˚
distances of 2.136(4) A seen in [calix[4](OMe)2(O)2Fe-
˚
(THF)], [71] 2.0941(19)
O2CAr)2(O2CAr)2(THF)2}, [72] and 2.071(6) A seen in
A
observed in {Fe2(m-
˚
Fe[N(SiMe3)2]2(THF) [34]. The closest FeÁ Á ÁF distance
˚
of 3.409(2) A (Fe(1)ꢀ
/
F(5)) is similar to that of 2.105(3)
˚
A seen for an ironÁ
/
hexafluoroantimonate interaction in
[Fe(TPP)][SbF6] (TPPꢁtetraphenylporphinato) [73].
/
2.2.5. Co[N(C6F5)2]2(py)2 (5)
Cooling a concentrated toluene solution of 5 to
Fig. 3. A thermal ellipsoid view of K{VCl[N(C6F5)2]3} (3) drawn with
30% probability ellipsoids, and giving the atom number scheme used in
the tables; only half of the dimer is shown. The interstitial toluene
molecule is omitted for clarity.
ꢃ35 8C yielded crystals of the cobalt complex that
/
were suitable for diffraction analysis. A thermal ellip-
soid drawing is shown in Fig. 5; relevant bond lengths
those previously reported for similar compounds, i.e.
˚
N distances of 1.934(2) and 1.988(2) A were observed
Vꢀ
/
˚
in V[N(SiMe3)2]2Ph(py) [60] 1.950(3) A (ave.) in [(Me3-
˚
Si)2N]2V(o-Me2NCH2C6H4) [60] 1.937(2)Á
V(NPh2)3(THF) [29] 1.988(7)Á2.004(7)
[Li(THF)4][V(NPh2)4] [61] and 1.94(2) A in [(Me3-
Si)2N]N[N(SiMe3)SiMe2CH2](py) [62]. The VꢀCl dis-
tance of 2.2999(12) A is similar to those observed in
{Li(TMEDA)2}{VCl2[N(SiMe3)2]2} (2.309(1) and
/1.961(2) A in
˚
A
/
in
˚
/
˚
˚
2.311(1) A), [63] (Ph2nacnac)VCl2(THF)2 (2.362 A)
˚
[64] and {NHEt3}{VCl2[C6H4-1,2-(NHCO-2-C5H4N)2}
˚
(2.350(1) and 2.357(1) A) [65]. The only significant
vanadiumÁ
fluorine contact in 3 is the V(1)Á Á ÁF(12)
interaction of 2.284(2) A, which may be compared
/
˚
˚
with that of 2.306(2) and 2.378(2) A in VCl[2,4,6-
(CF3)3C6H2]2(THF) [66]. KÁ Á ÁCl interactions of
˚
˚
˚
3.0925(14) A are similar to those of 3.269Á3.288 A in
/
[K(18-crown-6)]2[SeCl6] [67] 2.618(7) and 2.938(9) A in
{Th[Me3SiCHC(But)NSiMe3)]2(m3-Cl)(m-Cl)2K(OEt2)}n
[59] and the intermolecular KÁ Á ÁCl distances of
˚
3.0953(12) and 3.0946(11) A determined for 2.
2.2.4. Fe[N(C6F5)2]2(THF)2 (4)
Single crystals of 4 that were amenable to X-ray
diffraction were grown from a concentrated toluene
solution at ꢃ35 8C. A thermal ellipsoid view of the
/
structure is presented in Fig. 4; selected bond lengths
and angles are available in Table 4. The iron center sits
on a twofold rotation axis, and is coordinated in
Fig. 4. A thermal ellipsoid view of Fe[N(C6F5)2]2(THF)2 (4) drawn
with 30% probability ellipsoids, and giving the atom number scheme
used in the tables.

G.R. Giesbrecht et al. / Polyhedron 22 (2003) 153Á
/163
159
Table 4
Table 5
˚
˚
Selected bond distances (A) and angles (8) for Fe[N(C6F5)2]2(THF)2 (4)
Selected bond distances (A) and angles (8) for Co[N(C6F5)2]2(py)2 (5)
Bond lengths
Bond lengths
Fe(1)ꢀN(1)
Fe(1)ꢀF(5)
2.0495(19) Fe(1)ꢀO(1)
3.409(2)
2.1193(16)
Co(1)ꢀN(1)
Co(1)ꢀN(3)
Co(1)ꢀF(8)
1.989(3)
2.090(3)
2.507(2)
Co(1)ꢀN(2)
Co(1)ꢀN(4)
1.979(3)
2.053(3)
Bond angles
N(1)ꢀFe(1)ꢀN(1ꢀ)
N(1)ꢀFe(1)ꢀO(1ꢀ)
121.19(11) N(1)ꢀFe(1)ꢀO(1)
103.43(7)
132.40(9)
Bond angles
99.44(7)
O(1)ꢀFe(1)ꢀO(1ꢀ)
N(1)ꢀCo(1)ꢀN(2)
N(1)ꢀCo(1)ꢀN(4)
N(2)ꢀCo(1)ꢀN(3)
N(2)ꢀCo(1)ꢀF(8)
N(3)ꢀCo(1)ꢀF(8)
Co(1)ꢀF(8)ꢀC(8)
127.81(13) N(1)ꢀCo(1)ꢀN(3)
109.94(13) N(1)ꢀCo(1)ꢀF(8)
95.85(12) N(2)ꢀCo(1)ꢀN(4)
99.98(12)
73.6(1)
112.13(13)
107.09(12)
76.8(1)
87.4(1)
173.4(1)
106.1(2)
N(3)ꢀCo(1)ꢀN(4)
N(4)ꢀCo(1)ꢀF(8)
and angles are presented in Table 5. The solid-state
structure of 5 includes a molecule of toluene in the
crystal lattice. The coordination geometry about the
cobalt metal center approximates a trigonal bipyramid,
with N(3) and F(8) occupying axial positions, and N(1),
rate anion in [Co3(dpa)4Cl]BF4 (dpaꢁ
/
dipyridylamine)
[78].
N(2) and N(4) in the meridianal plane. The Coꢀ
/
˚
N(pyridine) distances of 2.090(3) and 2.053(3) A are
˚
comparable with those of 2.087(4) and 2.102(5) A seen
N(amide)
˚
distances of 1.989(3) and 1.979(3) A are slightly longer
than those observed in {Co[N(SiMe3)2]2}2 (1.922(5) and
3. Conclusions
in Co{[OC(CF3)2CH2]2S}(py)2 [74]. The Coꢀ
/
We have shown that the decafluorodiphenylamido
ligand is easily introduced to a wide variety of transition
metals by simple metathetical synthetic procedures.
Although early transition metals such as titanium,
zirconium and vanadium prefer to form anionic metal-
late complexes, this tendency is less pronounced for the
later transition metals. In the solid state, the decafluor-
odiphenylamido ligand displays a marked tendency to
form secondary interactions between the central metal
ion and ortho-fluorine atoms on the fluorophenyl
substituent. Although numerous examples of secondary
˚
1.910(5) A) [75] and [Co(NPh2)2]2 (1.889(8) A) [35]. The
˚
˚
CoÁ Á ÁF interaction of 2.507(2) A is longer than the
˚
cobalt-hexafluorosilicate CoÁ Á ÁF distance of 2.143(2) A
in [Co(NVI)4(m-SiF6)] (NVIꢁ
/
N-vinylimidazole) [76]
˚
but comparable to the CoÁ Á ÁF distance of 2.65(2) A
seen in Co[HB(3,5-Me2Pz)3](C6F5) [77]. Cotton and co-
˚
F distance of 2.223(5) A
workers have observed a Coꢀ
/
between a trinuclear cobalt cation and a tetrafluorobo-
Mꢀ
/
F interactions were discovered in the solid state,
these were not observed in solution, suggesting that such
interactions are probably weak and do not occur within
the coordination sphere of the metal under normal
reaction conditions. Thus, it can be seen that the highly
electron-withdrawing decafluorodiphenylamido ligand
may be used to support electrophilic transition metal
centers; these complexes may prove useful in applica-
tions such as olefin polymerization where such require-
ments are favorable.
4. Experimental
4.1. General considerations
All manipulations were carried out under an inert
atmosphere of oxygen-free UHP grade argon using
standard Schlenk techniques or under oxygen-free
helium in a Vacuum Atmospheres glove box. Deca-
fluorodiphenylamine [22] and TiCl3(THF)3 [79] were
prepared as described previously. ZrCl4 and VCl3 were
purchased from Strem Chemical Co. and used as
received. FeCl3 was obtained from Acros and used as
received. NaH and CoI2 were purchased from Aldrich
Fig. 5. A thermal ellipsoid view of Co[N(C6F5)2]2(py)2 (5) drawn with
30% probability ellipsoids, and giving the atom number scheme used in
the tables. The interstitial toluene molecule is omitted for clarity.

160
G.R. Giesbrecht et al. / Polyhedron 22 (2003) 153Á163
/
and used as received. Pyridine was purchased from
Aldrich and distilled over sodium prior to use. Toluene,
THF and hexanes were de-oxygenated by passage
through a column of supported copper redox catalyst
(Cu-0226 S) and dried by passing through a second
column of activated alumina. C6D6 and C7D8 were dried
4.1.2. {K(C7H8)2}{ZrCl2[N(C6F5)2]3} (2)
In the dry box, decafluorodiphenylamine (2.1 g, 6.0
mmol) was dissolved in 30 ml of THF and a slight excess
(0.33 g, 8.2 mmol) of potassium hydride was added. The
solution was stirred at r.t. for 10 min, until gas evolution
had subsided. Stirring was discontinued, and the excess
potassium hydride allowed to settle. The supernatant
potassium amide solution was removed with a pipette
and added to a slurry of ZrCl4 (0.47 g, 2.0 mmol) in 50
ml of THF. The reaction mixture was allowed to stir at
r.t. for 18 h and the resulting off-white suspension
filtered through a Celite pad. The filtrate was pumped to
dryness and the resulting solid was extracted with
toluene (100 ml). The solution was again filtered
through Celite and the filtrate reduced in volume to 10
over Naꢀ
/
K alloy, trap-to-trap distilled and degassed
before use. 1H NMR spectra were recorded on a Varian
Unity 300 spectrometer at ambient temperature; 1H
chemical shifts are given relative to residual C6D5H
(dꢁ
/
7.15 ppm) or C7D7H (dꢁ
2.09 ppm). 19F NMR
spectra were recorded on a Bruker DRX-500 spectro-
/
meter at ambient temperature; 19F chemical shifts are
given relative to external CFCl3 (dꢁ0.0 ppm). Infrared
/
spectra were recorded on a Digilab FTS-40 FT-IR
spectrometer; solid-state spectra were taken as Nujol
mulls between KBr plates, and calibrated against a
polyethylene standard. Elemental analyses were per-
ml before being placed in the freezer at ꢃ35 8C. Over a
/
period of several days, large colorless crystals were
deposited. The crystals were isolated by decanting the
mother liquor and allowing the crystals to dry in the dry
box atmosphere (1.7 g, 57% yield). 1H NMR (300 MHz,
formed on a PerkinÁElmer 2400 CHN analyzer. Ele-
/
mental analysis samples were prepared and sealed in tin
capsules in the glove box prior to combustion.
C6D6): only resonances for free toluene were observed.
19F NMR (470 MHz, C7D8): d ꢃ
3
/
111.9 (d, JFꢀF
ꢁ22.6
/
3
Hz, 8F, ortho-F), ꢃ
/
113.0 (d, JFꢀF
ꢁ22.6 Hz, 4F,
/
3
4.1.1. {Na(THF)2}{Ti[N(C6F5)2]4} (1)
ortho-F), ꢃ
/
124.7 (t, JFꢀF
ꢁ
/
22.6 Hz, 4F, para-F),
128.4 (t,
128.5 (t, JFꢀF 22.6
3
In the dry box, decafluorodiphenylamine (1.00 g, 2.9
mmol) was dissolved in 30 ml of THF and an excess
(0.20 g, 8.3 mmol) of sodium hydride was added. The
solution was stirred at room temperature (r.t.) for 10
min, until gas evolution had subsided. Stirring was
discontinued, and the excess sodium hydride allowed to
settle. The supernatant sodium amide solution was
removed with a pipette and added to a solution of
TiCl3(THF)3 (0.35 g, 1.0 mmol) in 50 ml of THF. The
reaction mixture was allowed to stir at r.t. for 18 h to
produce a deep green solution with some white pre-
cipitate. All solvent was removed in vacuo to leave a
greenish solid. This was washed with hexanes (30 ml)
and then extracted with toluene (50 ml). The toluene
extract was allowed to stand at r.t., producing large
blue/green crystals. These were decanted free from the
ꢃ126.3 (t, JFꢀF
/
ꢁ
/
22.6 Hz, 2F, para-F), ꢃ
/
3
3JFꢀF
ꢁ
/
22.6 Hz, 4F, meta-F), ꢃ
/
ꢁ
/
Hz, 8F, meta-F). IR (Nujol, cmꢃ1): 1633 (m), 1519 (s),
1303 (m), 1169 (w), 1145 (w), 1032 (s), 824 (w), 727 (s),
694 (m), 613 (m). Anal. Calc. for C43H8Cl2F30KN3Zr [2-
(toluene)]: C, 38.61; H, 0.60; N, 3.14. Found: C, 37.84;
H, 0.84; N, 2.98%.
4.1.3. K{VCl[N(C6F5)2]3} (3)
In the dry box, decafluorodiphenylamine (1.00 g, 2.9
mmol) was dissolved in 30 ml of THF and an excess
(0.15 g, 3.7 mmol) of potassium hydride was added. The
solution was stirred at r.t. for 10 min, until gas evolution
had subsided. Stirring was discontinued, and the excess
potassium hydride allowed to settle. The supernatant
potassium amide solution was removed with a pipette
and added to a slurry of vanadium trichloride (0.150 g,
1.0 mmol) in 50 ml of THF. The reaction mixture was
allowed to stir at r.t. for 18 h to produce a deep red
solution with some gelatinous precipitate. All solvent
was removed in vacuo to leave a dark solid. This was
washed with hexanes (30 ml) and then extracted with
toluene (50 ml). The extract was filtered through Celite
and the filtrate reduced in volume to 10 ml before 3 ml
of hexanes was added and the solution was placed in the
solution and stored under fresh toluene at ꢃ35 8C. The
/
remaining solution was filtered through Celite and the
filtrate reduced in volume to 30 ml, at which point, a
microcrystalline solid was being deposited. The solution
was heated to 50 8C to redissolve the solid, allowed to
stand at r.t., and then placed in the freezer. Overnight,
blue/green crystals were deposited. The crystals were
isolated by decanting the mother liquor and drying in
1
vacuo (0.26 g, 15% yield). H NMR (300 MHz, C6D6):
only resonances for free THF were observed. 19F NMR
(470 MHz, C7D8): due to the paramagnetism of 1, no
19F resonances were observed. IR (Nujol, cmꢃ1): 1659
(w), 1519 (s), 1366 (m), 1315 (w), 1266 (w), 1168 (w),
1032 (s), 982 (m), 844 (m), 722 (m), 667 (m). Anal. Calc.
for C48F40N4NaTi [1-2(THF)]: C, 39.40; N, 3.83.
Found: C, 37.94; N, 3.75%.
freezer at ꢃ35 8C. Overnight, clumps of very dark red
/
crystals were formed. The crystals were isolated by
decanting the mother liquor and then dried in vacuo
(0.55 g, 22% yield). 19F NMR (470 MHz, C7D8); due to
the paramagnetism of 3, no 19F resonances of the
complex were observed. IR (Nujol, cmꢃ1): 1643 (w),
1518 (s), 1306 (m), 1154 (w), 1032 (s), 982 (m), 824 (w),

G.R. Giesbrecht et al. / Polyhedron 22 (2003) 153Á
/163
161
727 (m), 660 (w). Anal. Calc. for C36ClF30KN3V: C,
36.96; N, 3.59. Found: C, 34.99; N, 3.86%.
IR (Nujol, cmꢃ1): 1606 (w), 1503 (s), 1306 (w), 1217
(m), 1024 (s), 980 (s), 827 (w), 754 (m), 726 (m), 699 (m),
610 (w). Anal. Calc. for C34H10CoF20N4: C, 44.71; H,
1.10; N, 6.13. Found: C, 43.34; H, 1.48; N, 5.80%.
4.1.4. Fe[N(C6F5)2]2(THF)2 (4)
In the dry box, decafluorodiphenylamine (1.00 g, 2.9
mmol) was dissolved in 30 ml of THF and an excess
(0.15 g, 3.7 mmol) of potassium hydride was added. The
solution was stirred at r.t. for 10 min, until gas evolution
had subsided. Stirring was discontinued, and the excess
potassium hydride allowed to settle. The supernatant
potassium amide solution was removed with a pipette
and added to a solution of FeCl3 (0.15 g, 1.0 mmol) in
50 ml of THF. The reaction mixture was allowed to stir
at r.t. for 18 h to produce a deep red/purple solution
with some precipitate. All solvent was removed in vacuo
to leave a dark solid. This was washed with hexanes (30
ml) and then extracted with toluene (50 ml). The extract
was filtered through Celite and the filtrate reduced in
volume to 10 ml before 5 ml of hexanes was added and
5. Crystallographic studies
The crystal structures of all compounds were deter-
mined as follows, with exceptions noted in subsequent
paragraphs: a crystal was mounted onto a glass fiber
using a spot of silicone grease. Due to air sensitivity, the
crystal was mounted from a pool of mineral oil under
argon gas flow. The crystal was placed on a Bruker P4/
CCD diffractometer, and cooled to 203 K using a
Bruker LT-2 temperature device. The instrument was
equipped with a sealed, graphite monochromatized Mo
˚
Ka X-ray source (lꢁ/0.71073 A). A hemisphere of data
was collected using 8-scans, with 30 s frame exposures
and 0.38 frame widths. Data collection and initial
indexing and cell refinement were handled using SMART
[80] software. Frame integration, including Lorentz-
polarization corrections, and final cell parameter calcu-
lations were carried out using SAINT [81] software. The
data were corrected for absorption using the SADABS
[82] program. Decay of reflection intensity was mon-
itored via analysis of redundant frames. The structure
was solved using Direct methods and difference Fourier
techniques. All hydrogen atom positions were idealized,
and rode on the atom they were attached to. The final
refinement [83] included anisotropic temperature factors
on all non-hydrogen atoms. Structure solution, refine-
ment, graphics, and creation of publication materials
were performed using SHELXTL NT [84]. Additional
details of data collection and structure refinement are
listed in Table 6.
the solution was placed in the freezer at ꢃ35 8C.
/
Overnight, pale purple/brown crystals were deposited.
The crystals were isolated by decanting the mother
liquor and drying in vacuo (0.46 g, 51% yield). 1H NMR
(300 MHz, C6D6): only resonances for free THF were
observed. 19F NMR (470 MHz, C7D8): due to the
paramagnetism of 4, no 19F resonances were observed.
IR (Nujol, cmꢃ1): 1658 (m), 1519 (s), 1346 (m), 1306
(m), 1268 (m), 1182 (m), 1137 (w), 1032 (s), 982 (s), 828
(m), 727 (m), 695 (m), 675 (w), 648 (w), 605 (w). Anal.
Calc. for C24F20FeN2 [4-2(THF)]: C, 38.33; N, 3.72.
Found: C, 37.30; N, 3.51%.
4.1.5. Co[N(C6F5)2]2(py)2 (5)
In the dry box, decafluorodiphenylamine (1.00 g, 2.9
mmol) was dissolved in 30 ml of THF and an excess
(0.20 g, 8.3 mmol) of sodium hydride was added. The
solution was stirred at r.t. for 10 min, until gas evolution
had subsided. Stirring was discontinued, and the excess
sodium hydride allowed to settle. The supernatant
sodium amide solution was removed with a pipette
and added to a solution of CoI2 (0.45 g, 1.4 mmol) in 50
ml of THF. The reaction mixture was allowed to stir at
r.t. for 18 h to produce a deep blue/green solution with
some white precipitate. The solution was filtered
through Celite, and the filtrate pumped dry to leave a
green/red dichroic oil. One milliliter of pyridine was
added to the oil, at which point it became blood red. The
pyridine was removed in vacuo, and the residue
dissolved in toluene (5 ml). This solution was layered
5.1. {Na(THF)2}{Ti[N(C6F5)2]4} (1)
A disordered lattice toluene was restrained to approx-
imate ideal geometry, and was refined with isotropic
thermal parameters. The toluene was disordered on an
inversion center, and the methyl group was refined at
one-half occupancy. Hydrogen atom positions were not
included on this toluene.
5.2. {K(C7H8)2}{ZrCl2[N(C6F5)2]3} (2)
with hexanes (5 ml) and placed in the freezer at ꢃ
/
35 8C.
A lattice toluene was found and refined with isotropic
thermal parameters, and without hydrogen atom posi-
tions. One of the toluene molecules bound to the
potassium ion was disordered, and the methyl group
was refined in three positions of one-third occupancy
each (C50A, C50B, and C50C). All toluene molecules
were restrained to approximate ideal geometry.
Very dark red crystals were deposited overnight. The
crystals were isolated by decanting the mother liquor
and drying briefly in vacuo (0.89 g, 63% yield). 1H NMR
(300 MHz, C6D6): only resonances for free pyridine
were observed. 19F NMR (470 MHz, C7D8): due to the
paramagnetism of 5, no 19F resonances were observed.

162
G.R. Giesbrecht et al. / Polyhedron 22 (2003) 153Á163
/
Table 6
Crystallographic data
a
Compound
1.toluene
2.toluene
3.toluene
4
5.toluene
Formula
MW
C
63H16F40N4NaO2Ti C57H24Cl2F30KN3Zr C86H16Cl2F60K2N6V2 C32H16F20FeN2O2
C41H18CoF20N2
1005.52
203(2)
1691.69
203(2)
1522.01
203(2)
monoclinic
P21/c
2524.03
203(2)
triclinic
896.32
203(2)
monoclinic
C2/c
Temperature (K)
Crystal system
Space group
monoclinic
C2/c
triclinic
¯
¯
P/
1
/
P/1/
˚
a (A)
22.3959(14)
14.9107(10)
20.0870(13)
90
19.3262(9)
16.5456(8)
18.8875(9)
90
12.2562(6)
15.3323(7)
24.3529(12)
104.708(1)
91.890(1)
90.659(1)
4423.0(4)
2
21.2537(14)
10.9811(7)
16.254(1)
90
11.8576(8)
12.3743(8)
14.600(1)
69.639(1)
83.229(1)
81.941(1)
1983.1(2)
2
˚
b (A)
˚
c (A)
a (8)
b (8)
g (8)
112.123(2)
90
103.129(1)
90
124.853(1)
90
3
˚
V (A )
Z
6214.0(7)
4
1.808
5881.7(5)
4
1.719
3113.0(3)
4
1.912
Dcalc (g mlꢃ1
)
1.895
0.545
2464
1.684
0.565
998
Absorption coefficient (mmꢃ1
F(000)
)
0.316
3324
0.486
3000
0.643
1776
u Range (8)
2.20Á
/
26.43
1.66Á
27 821
10 592 [Rintꢁ0.0234] 14 184 [Rintꢁ0.0305] 3029 [Rintꢁ0.0273] 6882 [Rintꢁ0.0225]
/
25.35
1.66Á
16 090
/
25.03
2.2Á
14 156
/
26.4
1.5Á
8865
/
26.4
Total reflections
Independent reflections
Goodness-of-fit
Final R indices
[I ꢀ2s(I)]
27 321
6136 [Rintꢁ0.053]
1.112
1.603
R1ꢁ0.0479
wR2ꢁ0.1449
0.964
R1ꢁ0.0503
wR2ꢁ0.1209
1.413
R1ꢁ0.0404
wR2ꢁ0.1116
1.160
R1ꢁ0.0576
wR2ꢁ0.1399
R1ꢁ0.0788
wR2ꢁ0.1272
a
R1ꢁajjFojꢃjFcjj/ajFoj and R2wꢁ[a[w(Fo2ꢃFc2)2]/a[w(Fo2)2]]1/2; wꢁ1/[s2(Fo2)ꢂ(aP)2], where aꢁ0.0292, 0.0630, 0.0713, 0.0557 and 0.0692
for compounds 1Á5, respectively.
/
5.3. K{VCl[N(C6F5)2]3} (3)
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and 0.0692.
/
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/
jFcjj/ajFoj and R2wꢁ
/
[a[w(Fo2ꢃ
/
Fc2)2]/a[w(Fo2)2]]1/
/
1/[s2(Fo2)ꢂ
/
(aP)2], where aꢁ
/
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