Synthesis and structures of dinuclear low-coordinate lithium and zirconium(IV) complexes derived from the diamido ligands 1,3-(CH2NC6H3R1 2)2C6H4(R1 = Me or Pri)

Article abstract of DOI:10.1039/b206508h

Treatment of 1,3-bis(bromomethyl)benzene with two equivalents of the appropriate compound Li[N(H)C₆H₃R¹₂-2,6] yielded the diamines 1,3-[CH₂N(H)C₆H₃R¹₂- 2,6]₂C₆H₄ 1 [R¹ = Me, abbreviated as H₂(D)] or 2 [R = Prⁱ, Abbreviated as H₂(D′)]. The crystalline complex [Li₂(D′)]₂ 3 was obtained from 2 and 2 LiBuⁿ; the analogue from 1 and 2 LiBuⁿ was an incompletely characterised oil. The binuclear, crystalline zirconium(IV) amides [{Zr(NMe₂)₃}₂(μ-D′)]4, its D analogue 5 and [{Zr(NMe₂)₂}₂(μ-D)₂]6 were prepared from [{Zr(NMe₂)₃(μ-NMe₂)}₂] and H₂(D′) [or 2 H₂(D′)], H₂(D) and 2 H₂(D), respectively. The single crystal X-ray molecular structures of complexes 3 and 4 have been elucidated. That of 3 comprises a sixteen-membered, twisted macrocyclic LiNC₅NLiNC₅N core with each of the two-coordinate lithium atoms part of the LiNLiN rhombus. The four-coordinate zirconium atoms in 4 are in an only slightly distorted tetrahedral environment, with the two Zr(NMe₂)₃ units arranged trans to one another across the central aromatic ring. None of 4-6, with MAO, showed catalytic activity for ethylene polymerisation under ambient conditions.

Full text of DOI:10.1039/b206508h

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Synthesis and structures of dinuclear low-coordinate lithium
and zirconium(IV) complexes derived from the diamido ligands
1
1
i
¯
1,3-(CH2NC6H3R 2)2C6H4 (R ؍ Me or Pr )
Stéphane Daniele,a Peter B. Hitchcock,a Michael F. Lappert,*a Terence A. Nileb
and Colette M. Zdanskib
a The Chemistry Laboratory, University of Sussex, Brighton, UK BN1 9QJ.
E-mail: m.f.lappert@sussex.ac.uk
b Department of Chemistry, UNC Greensboro, NC 27412, USA
Received 4th July 2002, Accepted 2nd September 2002
First published as an Advance Article on the web 30th September 2002
Treatment of 1,3-bis(bromomethyl)benzene with two equivalents of the appropriate compound Li[N(H)C6H3R1 -2,6]
2
yielded the diamines 1,3-[CH2N(H)C6H3R1 -2,6]2C6H4 1 [R1 = Me, abbreviated as H2(D)] or 2 [R = Pri, abbreviated as
2
H2(DЈ)]. The crystalline complex [Li2(DЈ)]2 3 was obtained from 2 and 2 LiBun; the analogue from 1 and 2 LiBun was
an incompletely characterised oil. The binuclear, crystalline zirconium() amides [{Zr(NMe2)3}2(µ-DЈ)] 4, its D
analogue 5 and [{Zr(NMe2)2}2(µ-D)2] 6 were prepared from [{Zr(NMe2)3(µ-NMe2)}2] and H2(DЈ) [or 2 H2(DЈ)], H2(D)
and 2 H2(D), respectively. The single crystal X-ray molecular structures of complexes 3 and 4 have been elucidated.
That of 3 comprises a sixteen-membered, twisted macrocyclic LiNC5NLiNC5N core with each of the two-coordinate
lithium atoms part of the LiNLiN rhombus. The four-coordinate zirconium atoms in 4 are in an only slightly
distorted tetrahedral environment, with the two Zr(NMe2)3 units arranged trans to one another across the central
aromatic ring. None of 4–6, with MAO, showed catalytic activity for ethylene polymerisation under ambient
conditions.
We have extended our researches on metal amides to
Introduction
diamides. Relevant to the present paper are studies on the
The results presented herein represent a continuation of our
synthesis, structures and selected reactions of the crystalline
long-standing interest both in the chemistry of metal and
lithium and zirconium complexes of the dianionic N,NЈ-
metalloid amides1 and in organic derivatives of the Group 4
disubstituted 1,2-, 1,3- and 1,4-benzenediamido ligands (A, AЈ,
metals.2
AЉ; Vi = CH᎐CH ), B and C: [Li (µ-A)] ,9 [{Li(µ-A)(thf )} {Li-
᎐
2
2
2
2
Bulky lithium amides LiNR1R2 are particularly useful
reagents: as ligand transfer species and as powerful proton-
abstractors, especially from acidic hydrocarbons, and as
reagents for the synthesis of compounds containing C–C
bonds;1,3 homochiral lithium amides also have a role in asym-
metric synthesis.4
((µ-thf )}2], [Li(thf )2(µ-A)Li(thf )], [{Li(tmen)}2(µ-A)], [{Li-
(µ-AЈ)(thf )}2(µ-Li)]2, [{Li(tmen)}2(µ-AЉ)], [Li(thf )2(µ-C)],10 [Zr-
(A)Cl2(tmen)],11 [Zr(AЈ)Cl2], [{Zr(AЉ)Cl(µ-Cl)(thf )}2], [{Zr(A or
AЉ)NMe2(µ-NMe2)}2], [{Zr(NMe2)3}2(µ-B)],12 [{Zr(NMe2)}2-
(µ-B)2] (IV), [{Zr(NMe2)3}2(µ-C)] and [{Zr(NMe2)}2(µ-C)2] (V);
throughout R = SiMe3. The above Zr–AЉ compounds (like IV
and V12) were shown to provide polyethylene of high average
molecular weight when treated with MAO.11
Zirconium() amides, or Ti() analogues, are valuable as
precursors for numerous M() derivatives by virtue of their
weak and polar Mδϩ–NδϪ bonds (M = Ti, Zr).1,2 Hence they are
amenable both for reactions with protic species and as sub-
strates for insertion reactions (e.g. of an isocyanate or carbon
dioxide), with implications for their role as catalysts,1,2 as in the
polymerisation of acrylonitrile by [Ti(NMe2)4].5 Group 4 metal
complexes containing diamido ligands, such as I,6 II,7 and III8
have recently come to the fore as active olefin polymerisation
procatalysts : I and II with methylaluminoxane (MAO) for both
ethylene and propylene, while III with B(C6F5)3 induced the
living polymerisation of hex-1-ene.
A previous collaboration between the Sussex and Greens-
boro groups related to aspects of the chemistry of compounds
[YbCpx ] [Cpx = η5-C5H3(R1)-1-{CMe2(CH2)nC5H4N-2}-3; R1 =
2
H or R and n = 0 or 1].13
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J. Chem. Soc., Dalton Trans., 2002, 3980–3984
This journal is © The Royal Society of Chemistry 2002
DOI: 10.1039/b206508h

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Table 1 Selected bond lengths [Å] and angles [Њ] for complex 3
Results and discussion
The principal objective of the present study was to investigate
the effects of a less rigid diamido ligand backbone than those
of A–C on the preparation, structure and properties of lithium
and zirconium derivatives. Hence attention focused on the lig-
ands D and DЈ. The latter, in particular, resembles that present
in II,7 but without incorporating the nitrogen heteroatom.
The diamines H2(D) 1 and H2(DЈ) 2 were prepared (Scheme 1)
Li(l)–N(l)
1.909(4)
1.937(4)
2.393(8)
1.413(3)
1.422(3)
Li(l)–N(1)Ј
Li(2)–N(2)Ј
Li(2) ؒ ؒ ؒ Li(2)Ј
N(1)–C(1)
2.013(4)
1.988(4)
2.341(8)
1.467(3)
1.470(3)
Li(2)–N(2)
Li(l) ؒ ؒ ؒ Li(l)Ј
N(1)–C(9)
N(2)–C(21)
N(2)–C(5)
N(1)–Li(1)–N(1)Ј
Li(1)–N(1)–Li(1)Ј
104.1(2)
75.1(2)
N(2)–Li(2)–N(2)
Li(2)–N(2)–Li(2)Ј
106.3(2)
73.2(2)
The lithium atoms are in a two-coordinate environment and
range from 1.909(4) to 2.013(4) Å for Li2–N1 and Li1–N1Ј,
respectively. There are some close (< 2.80 Å) Li ؒ ؒ ؒ C contacts
(Fig. 2), but their relative spatial distribution is such that they
are unlikely to have agostic implications.
Scheme 1 Synthesis of compounds 1 and 2.
by the metathetical reaction between 1,3-bis(bromomethyl)-
benzene and two equivalents of the appropriate 2,6-dialkyl-
benzeneamidolithium (prepared in situ from 2,6-R1 C6H3NH2
2
and LiBun). They were purified by column chromatography (1)
or recrystallisation from light petroleum (2), as an orange oil
(1) or a cream powder (2) and were characterised by NMR
spectroscopy in solution, mass spectrometry and for 2 micro-
analysis.
Treatment of 2 with two equivalents of n-butyllithium
furnished the hydrocarbon-soluble, pyrophoric, colourless,
crystalline macrocycle [Li2(DЈ)]2 3. A similar experiment using
1 and 2 LiBun yielded a pyrophoric, labile compound, which
was not adequately characterised.
Fig. 2 Li environments showing shortest Li ؒ ؒ ؒ C (< 2.80 Å) contacts
for compound 3: Li1 ؒ ؒ ؒ C3 (2.649 Å), Li1 ؒ ؒ ؒ C9Ј (2.378 Å),
Li1 ؒ ؒ ؒ C10Ј (2.629 Å), Li1 ؒ ؒ ؒ C15Ј (2.579 Å), Li1 ؒ ؒ ؒ C16Ј (2.786
Å), Li2 ؒ ؒ ؒ C3 (2.652 Å), Li2 ؒ ؒ ؒ C4 (2.726 Å), Li2 ؒ ؒ ؒ C21Ј (2.477 Å),
Li2 ؒ ؒ ؒ C22Ј (2.707 Å), Li2 ؒ ؒ ؒ C27Ј (2.667 Å).
Although there appear to be eight previously published
structures for tetranuclear lithium amides free from a neutral
coligand, the structure of 3 is distinct and different from each.
Complex 3 shares with just one of them VI14 the presence of
two-coordinate lithium atoms, each bound to two nitrogen
The molecular structure of 3 was investigated both in the
crystal by X-ray crystallography and in toluene solution by
NMR spectroscopy. The C2-symmetric crystalline 3 (Fig. 1) has
atoms. The presence of a pair of LiNLiN rhombi is a feature
not only of complex 3 but also of the six complexes of the
general formulae VII;15–19 however, in the latter each three-
coordinate lithium atom is bound to three adjacent nitrogen
atoms. Complex VIII also has two such LiN3 environments and
a single but puckered [torsion angle 14.6(4)Њ] LiNLiN ring, and
otherwise is unique.9,20 The average Li–N distance of 1.96 Å in 3
is shorter than in VI [2.00(2) Å],14 VII [average Li–N/ Å: 2.01
a,15 2.06 b,16 2.01 c,17 2.06 d,18 2.09 e,9 2.06 f19] or VIII [2.12 Å
for the central Li atoms].9 In the LiNLiN rings, as in 3, the
mean of angles subtended at the nitrogen atoms are narrower
than those at the lithium atoms [average at N and Li : 68.4 and
101.3Њ (VIIa),15 68.8 and 111Њ (VIIb),16 70.6 and 109Њ (VIIc),17
70.7 and 108.5Њ (VIId),18 82.5 and 108.7Њ (VIIe)9 and 71.7 and
108.7Њ (VIIf )19].
Fig. 1 Molecular structure of compound 3.
1
The H and 13C{1H} NMR spectra of 3 in toluene-d8 dis-
played only one set of Pri resonances and a singlet at δ 9.03
attributed to C(3)H and a broad feature at δ 0.8 (w1/2 = 112.5
Hz) assigned to CH(CH3)2. At 203 K, the latter split into a 1 : 1 :
1 : 1 multiplet and CH(CH3)2 protons give rise to four septets,
consistent with the solid state structure (there are 8 Pri groups
of which 4 are unique). In addition, the CH2 signal shifted from
δ 4.34 to δ 4.93 at 203 K. The 7Li{1H} NMR spectrum at 293 K
showed a sharp signal at δ 1.84. From a heteronuclear 7Li{1H}
a sixteen-membered twisted macrocyclic LiNC5NLiNC5N core;
selected geometric parameters are in Table 1. Each of these two
lithium atoms is part of a LiNLiN rhombus, with the angle at
the lithium atoms [104.1(2)Њ at Li1 and 106.3(2)Њ at Li2] wider
than those at the nitrogen atoms [75.1(2)Њ at N1 and 73.2(2)
at N2]. The inter-planar angles between Li1–N1–Li1Ј and Li1–
N1’–Li1’or Li2–N2–Li2Ј and Li2–N2Ј–Li2Ј are 9.2 or 7.9Њ,
respectively. The N-centred 2,6-diisopropylphenyl rings are
orthogonal to the macrocycle, with average CNCC torsion
angles of 90.1Њ.
7
study, it is evident that at ambient temperature the Li nucleus
interacted with both HCMe2 and HC(3) 1H nuclei, the 7Li
J. Chem. Soc., Dalton Trans., 2002, 3980–3984
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signal enhancements being 24 and 6% respectively. The
1J[13C(3)–1H] was smaller for 3 (143 Hz) than in the parent
diamine 2 (154 Hz). These features indicate that the close
Li ؒ ؒ ؒ C contacts observed in the solid state may well also be
present in solution.
Fig. 3 Molecular structure of compound 4.
Table 2 Selected bond lengths [Å] and angles [Њ] for complex 4
The reactions between [{Zr(NMe2)3(µ-NMe2)}2]21 and the
diamine H2(D) 1 or H2(DЈ) 2, yielding the binuclear zircon-
ium() amides 4–6 are shown in Scheme 2. In the case of 1, the
Zr(1)–N(1)
Zr(1)–N(3)
Zr(2)–N(5)
Zr(2)–N(7)
N(1)–C(1)
N(5)–C(21)
2.098(7)
2.057(7)
2.093(7)
2.043(7)
1.447(10)
1.437(10)
Zr(1)–N(2)
Zr(1)–N(4)
Zr(2)–N(6)
Zr(2)–N(8)
N(1)–C(13)
N(5)–C(20)
2.024(7)
2.029(7)
2.019(8)
2.025(7)
1.468(11)
1.483(11)
N(1)–Zr(1)–N(2)
N(1)–Zr(1)–N(4)
N(2)–Zr(1)–N(4)
N(5)–Zr(2)–N(6)
N(5)–Zr(2)–N(8)
N(6)–Zr(2)–N(8)
Zr(1)–N(1)–C(1)
C(1)–N(1)–C(13)
Zr(2)–N(5)–C(21)
114.0(3)
110.0(3)
108.2(3)
113.6(3)
111.6(3)
106.1(3)
108.5(5)
111.4(7)
115.8(6)
N(1)–Zr(1)–N(3)
N(2)–Zr(1)–N(3)
N(3)–Zr(1)–N(4)
N(5)–Zr(2)–N(7)
N(6)–Zr(2)–N(7)
N(7)–Zr(2)–N(8)
Zr(1)–N(1)–C(13)
Zr(2)–N(5)–C(20)
C(20)–N(5)–C(21)
112.2(3)
104.8(3)
107.2(3)
112.4(3)
105.1(3)
107.6(3)
140.1(5)
133.8(5)
110.4(7)
trend in other ZrIV(NMe2)(NAr) compounds: in [{Zr(A or
AЈ)NMe2(µ-NMe2)}2] the terminal Zr–NMe2 bonds and lengths
are 2.037(2) or 2.021(5) Å compared with mean Zr–Naryl bond
lengths of 2.107 or 2.114 Å, respectively;11 while in IV and V the
corresponding values are 2.031(2) or 2.026(2) Å and 2.094(2) or
2.086(2) Å.12 The four-coordinate zirconium atoms are in an
only slightly distorted tetrahedral environment, the N–Zr–NЈ
angles ranging from 104.8(3) to 114.0(3)Њ, the angles to
NC6H3Pri2-2,6 being the widest. Each nitrogen atom is in a
distorted trigonal planar environment, the Zr–N–CH2 angle
being the widest, 140.1(5) for Zr1 and 133.8(5)Њ for Zr2. It is
interesting that while 4 is a monomer, [{Zr(NMe2)3(µ-NMe2)}2]
is a dimer with the Zr atoms in a distorted trigonal bipyramidal
environment, the terminal equatorial and axial bond lengths
being 2.050(5) and 2.104(5) Å, respectively.21
Scheme 2 Synthesis of compounds 4–6. Reagents and conditions: (i) 1
equiv. of 1 or 2 in toluene at 20 ЊC; (ii) for R1 = Me, 1 equiv. of 1 in
toluene at 20 ЊC; (iii) 2 equiv. of 1 in toluene at 20 ЊC.
outcome was stochiometry-dependent. Thus, using a 1 : 1 molar
ratio of reagents, the product (i in Scheme 2) was the acyclic
zirconium compound 5; whereas from 2H2(D), the macrocyclic
complex 6 was obtained (iii in Scheme 2). By contrast, when
employing a large excess of the bulkier diamine 2, the acyclic
zirconium() amide 4 (i in Scheme 2), an analogue of 5, was
invariably formed. Presumably steric hindrance precluded a
further reaction of 4 with more H2(DЈ), as also evident from 1H
NMR spectroscopic data on 4 and 5, vide infra.
The molecular structure of the acyclic binuclear zircon-
ium() amide 4 is illustrated in Fig. 3 and selected geometric
parameters are listed in Table 2. The two zirconium atoms (each
bound to three NMe2 groups) are bridged by a [N(C6H3Pri2-
2,6)CH2C]2CH moiety; the three internal carbon atoms C14,
C15 and C18 are members of the central benzene ring. The two
Zr(NMe2)3 units are arranged trans to one another. The Zr–
NMe2 bond lengths range from 2.019(8) to 2.057(7) Å and are
slightly shorter than the Zr–NC6H3Pri2-2,6 bonds of 2.093(7)
and 2.098(7) Å. This is consistent with the previously observed
We propose, partly by analogy with structures of crystalline
4, IV12 and V, that D functions as a bridging ligand not only in
4 but also in 6 and thus differs from the chelating behaviour of
the diamido ligands in I6 or II.7
The 1H and 13C{1H} NMR spectra in toluene-d8 or C6D6 (6)
at 293 K were consistent with the structures shown in Scheme 2.
The 1H NMR spectra of the 2,6-dimethylphenylamides 5 and 6
showed singlets for the NMe2 protons, indicative of there being
unhindered rotation about the Zr–NMe2 bonds on the NMR
time scale. By contrast, the spectrum of the 2,6-diisopropyl-
phenylamides 4 at ambient temperature showed the HCMe2
signals as two separate 1 : 1 doublets.
Attempts to convert any of the amides 4–6 to chlorides
by replacing NMe2 groups by chlorides, using an excess of
trimethyl(chloro)silane proved unsuccessful. Likewise none of
4–6, with MAO, proved to be a catalyst for the polymerisation
of ethylene under ambient conditions.
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J. Chem. Soc., Dalton Trans., 2002, 3980–3984

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3
1H NMR (toluene-d8, 203 K): δ 0.31 [d, J(1H–1H) = 6.5, 6 H,
CH3], 0.61 [d, 3J(1H–1H) = 6.5, 6 H, CH3], 1.23 [d, 3J(1H–1H) =
6.5, 6 H, CH3], 1.37 [d, 3J(1H–1H) = 6.5, 6 H, CH3], 3.13 [sept,
Experimental
General procedures
3
3J(1H–1H) = 6.5, 1 H, CH], 3.22 [sept, J(1H–1H) = 6.5, 1 H,
All manipulations were carried out under argon or dinitrogen
(1, 2) in flamed Schlenk-type glassware on a dual manifold
Schlenk line. Solvents were dried over sodium wire. Hydro-
carbons (pentane, hexane and toluene) or diethyl ether and
tetrahydrofuran solvents were distilled from sodium/potassium
alloy or sodium benzophenone, respectively, and stored over
sodium mirrors. Deuteriated solvents (benzene-d6, toluene-d8
and thf-d8) were distilled and degassed prior to use. 2,6-
Diisopropylaniline was purchased from Aldrich and was freshly
vacuum-distilled. All other reagents (Aldrich) were used without
further purification. The compound [{Zr(NMe2)3(µ-NMe2)}2]
was prepared as described in the literature.21 NMR spectra were
recorded on Bruker DPX 300 or AMX 500 instruments at
293 K unless otherwise stated, and were referenced internally
(1H, 13C) to residual solvent resonances or externally (7Li). The
electron impact mass spectra were recorded on solid samples
using a Kratos MS 80 or (1, 2) a Fisons WG-Autospec
instrument. Elemental analyses were carried out by Medac Ltd
(UK) (4–6) or (2) Desert Analytics, Tucson, Arizona.
CH], 3.68 [sept, J(1H–1H) = 6.5, 1 H, CH], 3.79 [sept, J(1H–
1H) = 6.5 Hz, 1 H, CH], 4.93 [s, 4 H, CH2], 6.94–7.11 [m, 9 H,
aromatic], 9.11 [s, 1 H, CH]; 13C{1H} NMR (toluene-d8): δ 25.0
[br, w1/2 = 187 Hz, CH3], 27.8 (CH), 63.2 (CH2), 120.0, 123.0,
124.4, 127.4, 132.4, 146.8, 148.2 and 153.7 (aromatic); 7Li{1H}
NMR (toluene-d8): δ 1.84 (br, w1/2 = 97 Hz).
3
3
The dinuclear open-chain zirconium(IV) amide 4. The diamine
2 (0.844 g, 1.85 mmol) in toluene (10 cm3) was added dropwise
during ca. 10 min to a solution of [{Zr(NMe2)3(µ-NMe2)}2]
(0.59 g, 1.85 mmol) in toluene (30 cm3) at 0 ЊC. The deep yellow
mixture was stirred at room temperature for ca. 20 h, whereafter
solvent was removed in vacuo and pentane (30 cm3) was added.
The mixture was filtered. The filtrate was concentrated (to ca.
10 cm3) and set aside at Ϫ35 ЊC. Three crops of the pale yellow,
crystalline complex 4 (1.15 g, 79%) (Found: C, 58.2; H, 8.39; N,
12.51. C44H74N8Zr2 requires C, 58.9; H, 8.31; N, 12.48%) were
isolated by filtration and drying in vacuo. 1H NMR (toluene-d8):
δ 1.12 [d, J(1H–1H) = 6.5, 12 H, CCH3], 1.21 [d, J(1H–1H) =
6.5, 12 H, CCH3], 2.75 [s, 36 H, NCH3], 3.59 [sept, 3J(1H–1H) =
6.5 Hz, 4 H, CH], 4.48 [s, 4 H, CH2], 7.04–7.21 [m, 10 H,
aromatic]; 13C{1H} NMR (toluene-d8): δ 24.6 and 25.7 (CCH3),
28.1 (CH), 41.7 (NCH3), 61.6 (CH2), 124.3, 125.8, 126.2, 128.8,
131.7, 141.2, 144.0 and 148.1 (aromatic C). MS [m/z (%,
assignment)] : 855 (53, [M Ϫ Pri]ϩ); 812 (39, [M Ϫ 2Pri]ϩ).
3
3
Preparations
1,3-Bis(2Ј,6Ј-dimethylphenylaminomethyl)benzene 1. n-Butyl-
lithium (18.9 cm3 of a 2.0 mol dmϪ3 solution in hexane, 37.9
mmol) was added to 2,6-dimethylaniline (2.77 g, 37.9 mmol) in
thf (75 cm3) at 0Њ C with stirring. The mixture was brought to
room temperature and was stirred for 30 min, then transferred
into a dropping funnel, from which it was added dropwise
to 1,3-bis(bromomethyl)benzene (5.00 g, 18.9 mmol) in thf
(100 cm3) at 0 ЊC. The mixture was set aside at room temper-
ature for ca. 48 h. Water (100 cm3) was added and the mixture
was extracted with diethyl ether (2 × 50 cm3). The ethereal layer
was dried and volatiles were removed in vacuo. Purification was
carried out using an alumina chromatography column with
light petroleum (bp 40–60 ЊC) as eluant. Removal of volatiles
The dinuclear open-chain zirconium(IV) amide 5. Using a
procedure similar to that described for 4 [from the diamine 1
(0.31 g, 0.9 mmol) and [{Zr(NMe2)3(µ-NMe2)}2] (0.48 g,
0.9 mmol) in toluene (6 cm3)] there were obtained two crops of
yellow crystals of 5 (0.53 g, 71%) (Found: C, 57.55; H, 6.82; N,
13.47. C40H58N8Zr2 requires C, 57.7; H, 6.97; N, 13.45%), mp
1
112 ЊC. H NMR (toluene-d8): δ 2.19 [s, 12 H, CCH3], 2.74 [s,
3
36 H, NCH3], 4.35 [s, 4 H, CH2], 6.81 [t, J(1H–1H) = 7.37 Hz,
1
3 H, aromatic], 6.92–7.06 [m, 7 H, aromatic]; 13C{1H} NMR
(toluene-d8, 293K): δ 18.8 (CCH3), 41.0 (NCH3), 58.4 (CH2),
123.6, 125.8, 127.7, 128.4, 130.3, 136.7, 141.9 and 148.8 (aro-
matic). MS [m/z (%, assignment)]: 344 (100, [1]ϩ).
from the eluate yielded 1 (4.37 g, 67.1%) as an orange oil. H
NMR (CDC13): δ 2.40 (s, 12 H, CH3), 3.29 (s, 2 H, NH), 4.29 (s,
4 H, CH2), 7.45–6.90 (m, 10 H, aromatic). MS (m/z): 344 [1]ϩ.
1,3-Bis((2,6-diisopropylphenyl)aminomethyl)benzene 2. Using
a procedure similar to that described for 1 [from n-butyllithium
(15.2 cm3 of a 2.5 mol dmϪ3 solution in hexane, 37.9 mmol),
2,6-diisopropylaniline (7.0 cm3, 37.9 mmol), thf (100 cm3) and
1,3-bis(bromomethyl)benzene (5.00 g, 18.9 mmol)], there was
obtained a light orange oil which, upon crystallisation from a
light petroleum solution, yielded 2 (4.29 g, 50%) (Found : C,
83.75; H, 9.60; N, 6.01. C32H44N2 requires C, 84.2; H, 9.71; N,
The dinuclear macrocyclic zirconium(IV) amide 6. Using a
procedure similar to that described for
4 [from the
diamine 1 (1.48 g, 4.32 mmol) and [{Zr(NMe2)3(µ-NMe2)}2]
(1.16 g, 2.16 mmol) in toluene (15 cm3)] there were obtained two
crops of yellow crystals of 6 (1.03 g, 55%) (Found: C, 64.2; H,
7.16; N, 10.88. C28H38N4Zr requires C, 64.4; H, 7.34; N,
10.73%), mp 125–126 ЊC. 1H NMR (toluene-d8): δ 2.12 [s, 12 H,
CCH3], 2.62 [s, 12 H, NCH3], 4.61 [s, 4 H, CH2], 6.56 [s, 1 H,
aromatic], 6.85–7.01 [m, 9 H, aromatic]; 13C{1H} NMR
(toluene-d8): δ 19.5 (CCH3), 41.6 (NCH3), 56.5 (CH2), 124.2,
128.0, 128.9, 129.3, 130.9, 136.0, 140.6 and 147.6 (aromatic).
MS [m/z (%, assignment)] : 344 (100, [1]ϩ).
1
6.31%). H NMR (CDC13): δ 1.15 [d,3J(1H–1H) = 6.85, 24 H,
CH3], 3.07 [s, 2 H, NH], 3.29–3.19 [sept, 3J(1H–1H) = 6.85, 4 H,
1
CH], 3.97 [s, 4 H, CH2], 7.27–7.01 [m, J(1H–13C(3)) = 154 Hz,
10 H, aromatic]. 13C{1H}: δ 24.8 (CH3), 28.3 (CH), 56.6 (CH2),
124.2, 124.7, 127.4, 127.9, 129.4, 141.1, 143.3 and 143.4
(aromatic). MS (m/z): 456 [2]ϩ.
Crystallography
The dinuclear macrocyclic lithium amide 3. n-Butyllithium
(1.6 cm3 of a 1.6 mol dmϪ3 solution in hexane, 2.59 mmol) was
added dropwise by syringe to the 1,3-di(arylphenylamino-
methyl)benzene 2 (0.591 g, 1.30 mmol) in hexane (10 cm3) at
0 ЊC. The mixture was brought to room temperature with stir-
ring for 2 h, yielding a white precipitate and a green supernatant
liquor. The mixture was filtered and the precipitate was dis-
solved in warm (80 ЊC) toluene (15 cm3). Cooling to room
temperature afforded colourless crystals of 3 (0.54 g, 88%).
1H NMR (toluene-d8): δ 0.8 [br s, w1/2 = 112.5 Hz, 24 H, CH3],
3.26 [sept, 3J(1H–1H) = 6.5, 4 H, CH], 4.34 [s, 4 H, CH2], 6.88–
7.08 [m, 1J(1H–13C(3)) = 143, 9 H, aromatic], 9.03 [s, 1 H, o-CH];
Data sets for 3 and 4 were collected on an Enraf-Nonius CAD4
diffractometer at 173
K using monochromated Mo-Kα
radiation. A single crystal was coated in mineral oil and cooled
in a stream of nitrogen gas. Corrections for absorption were
made using ψ-scan measurements. Structure solutions were
made using SHELXS-86.22 Refinement was based on F 2, with
H atoms in riding mode, using SHELXL-9723 with Uiso(H) of
1.2Ueq(C) or 1.5Ueq(C) for methyl groups. Further details for
3 and 4 are found in Table 3.
CCDC reference numbers 187959 (3) and 187960 (4).
See http://www.rsc.org/suppdata/dt/b2/b206508h/ for crystal-
lographic data in CIF or other electronic format.
J. Chem. Soc., Dalton Trans., 2002, 3980–3984
3983

View Article Online
Table 3 Crystal data and refinement for complexes 3 and 4
3
4
Formula
Formula weight
C64H84Li4N4
937.1
C44H74N8Zr2
897.5
Crystal system
Space group
a/Å
Monoclinic
C2/c (no.15)
21.045(6)
Triclinic
P1 (no.2)
11.315(4)
¯
b/Å
c/Å
15.874(3)
18.651(3)
12.706(6)
18.040(7)
α/Њ
β/Њ
90
115.79(2)
75.53(4)
77.94(3)
γ/Њ
90
5610(2)
0.06
84.97(3)
2454(2)
0.46
U/Å3
µ/mmϪ1
Z
4
2
6799
4020
Unique reflections, Rint
Reflections with I > 2σ(I)
Final R indices (for I > 2σ(I))
R indices (all data)
3688, 0.017
2564
R1 = 0.048, wR2 = 0.104
R1 = 0.079, wR2 = 0.118
R1 = 0.068, Rw = 0.139
R1 = 0.136, wR2 = 0.168
7 F. Guérin, D. H. McConville and J. J. Vittal, Organometallics, 1996,
15, 5586.
Acknowledgements
8 J. D. Scollard and D. H. McConville, J. Am. Chem. Soc., 1996, 118,
10008.
9 S. Daniele, C. Drost, B. Gehrhus, S. M. Hawkins, P. B. Hitchcock,
M. F. Lappert, P. G. Merle and S. G. Bott, J. Chem. Soc., Dalton
Trans., 2001, 3179.
We are grateful to the European Commission for the award of
a Marie Curie fellowship to S. D. and to Dr A. G. Avent for
useful NMR discussions.
10 L. J.-M. Pierssens, D. Phil Thesis, University of Sussex, 1997.
11 S. Daniele, P. B. Hitchcock, M. F. Lappert and P. G. Merle, J. Chem.
Soc., Dalton Trans., 2001, 13.
12 S. Daniele, P. B. Hitchcock and M. F. Lappert, Chem.Commun.,
1999, 1909.
13 J. R. van den Hende, P. B. Hitchcock, M. F. Lappert and T. A. Nile,
J. Organomet. Chem., 1994, 472, 79.
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J. Chem. Soc., Dalton Trans., 2002, 3980–3984