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In this work nine lithium N,N′-bis(trimethylsilyl)amidinates-TMEDA complexes and the dimeric adduct
of 2-ethylbenzonitrile lithium bis(trimethylsilyl)amide were synthesized and characterized. The later
compound was found to be a kinetically stabilized intermediate in the amidinate formation. The solid
state structures of the amidinates revealed several types of crystalline supramolecular structures, generated
by the degree and nature of involvement of the amidinate π system in the intermolecular interactions.
The π system was also found to play a significant role in the intramolecular bonding with the lithium
atom. The π bonding is obtained at the expense of the σ bond, weakening it, while keeping the metal–ligand
bond length almost invariable. This facile π interaction along with the Li-N σ-bond activation can imply
that similar involvements of the π systems may take place in the salt metathesis reactions with these
compounds.
Table 4. Key Bond Lengths [Å] and Angles [deg] for Complexes 5 Table 5. Selected Bond Lengthes [Å] and Angles [deg] for
and 7 Complex 6
complex 7a complex 7b complex 5 complex 6a complex 6b
Bond Lengths Bond Lengths
N(1)-C(1) 1.326(5) 1.333(5) 1.323(3) N(1)-C(1) 1.324(6) 1.326(6)
N(2)-C(1) 1.333(4) 1.315(4) 1.337(3) N(2)-Li(1) 2.009(9) 2.034(9)
N(1)-Li(1) 2.014(7) 2.028(7) 2.017(4) N(1)-Li(1) 1.997(9) 2.031(9)
N(2)-Li(1) 2.018(8) 2.017(7) 2.025(5) N(2)-C(1) 1.323(6) 1.325(6)
N(3)-Li(1) 2.110(10) 2.089(10) 2.091(5) N(3)-Li(1) 2.098(10) 2.090(10)
N(4)-Li(1) 2.087(9) 2.082(9) 2.106(5) N(4)-Li(1) 2.102(9) 2.075(10)
Bond Angles Bond Angles
N(1)-C(1)-N(2) 119.6(3) 120.7(3) 119.6(2) N(1)-C(1)-N(2) 123.0(4) 120.9(4)
N(1)-Li(1)-N(2) 69.5(2) 69.3(2) 69.33(16) N(1)-Li(1)-N(2) 71.0(3) 69.1(3)
Li(1)-N(1)-C(1)-N(2) 10.9(5) 9.0(5) 17.3(5) Li(1)-N(1)-C(1)-N(2) 8.1(5) 12.0(5)
N(1)-C(1)-C(2)-C(3) 88.1(5) 86.8(5) 86.2(5) N(1)-C(1)-C(2)-C(3) 80.6(5) 88.3(5)
is formed by two independent molecules in which the methoxy Table 6. Intermolecular Contact Distances [Å] and Angles [deg] in
Complexes 5-7
group of the first interacts with the NCN core of the second. In
addition, the meta hydrogen H(4b) of the second molecule complex 5 complex 6 complex 7
interacts with one of the nitrogens of the NCN core in a third C(20)-O(1) 3.612(5) H(4b)-N(2a) 2.89(9) C(20b)-N(2a) 3.726(7)
molecule that is equivalent to the first one producing the C(8)-N(2) 3.579(5) C(8a)-N(4b) 3.471(9) C(20b)-O(1a) 3.493(7)
O(1a)-C(8b) 3.697(9) C(8a)-N(1b) 3.727(7)
polymeric interaction (H(4b)-N(2a) ) 2.89 Å, C(4b)-H(4b)- O(1b)-C(13a) 3.564(9) C(8a)-O(1b) 3.311(7)
N(2a) ) 168°). In addition, the methoxy group of the second O(1b)-C(13b) 3.582(9) O(1a)-C(8a)-O(1b) 172.0(5)
molecule interacts with three different molecules (two TMEDA C(4b)-H(4b)-N(2a)
168.2(5)
methylene groups and an additional methoxide oxygen) produc-
ing the cross-linkage between the columns.
It is worth mentioning that complex 1317 also has a polymeric
in intermolecular interactions has a negligible effect on the
structure, governed by C · · · F contacts in the range of 3.4–3.6
N-C bond lengths (1.315-1.337 Å) and on the N-C-N
Å. All of the ring fluorine atoms participate in these interactions
with TMEDA methyl and methylene, and even with TMS bond angels (119.6-122.9°), the major influence is on the
methyl groups. metal coordination mode, expressed in the slippage of the
Effect of the Packing Interactions on the Intramolecular Li atom and the corresponding chelating TMEDA as regards
Structures. While the participation of the amidinate π system to the amidinate ligand plane. The extent of this slippage,
measured by the value of the Li-N-C-N dihedral angle,
increases with the strengthening of the amidinate intermo-
lecular interaction (Figure 9), which is evaluated by the
shortest distance between an NCN core nitrogen and a carbon
atom from a neighboring molecule.
The slippage of the Li atom from the NCN plane takes place
in two different vectors: perpendicularly and toward the amidi-
nate system, while the Li-N bond lengths remain unaffected
(Figure 10).
In complex 5 (Figure 7a), for example, which has the largest
dihedral angle, these movements are 0.596 and 0.098 Å,
respectively. The TMEDA moiety, on the other hand, moves
upward with the Li atom and keeps its perpendicularity with
respect to the amidinate plane. It is important to point out that
the Li-TMEDA distances and angles remain almost unchanged.
We suggest, therefore, that the weakening of the Li-N σ bond
in the amidinate ligand, obligated from the increased angular
strain, is compensated by a concurrent donation from the π
system. This shift in coordination mode is probably due to the
growing degree of steric hindrance between TMEDA and the
interacting fragment. Interestingly, the nitrogen in lithium
anilides40,41 also shows mixed σ/π donation to lithium. In these
systems the p character in the bonding to lithium was shown to
be affected by the electronic properties of the aromatic substit-
uents as well as by intramolecular steric factors. Steric hindrance
Figure 8. (a) ORTEP diagram of the molecular structure of complex
6 (50% thermal ellipsoids). Methyl groups on silicon and all
noninteracting hydrogen atoms are omitted for clarity. (b) Four (39) Chivers, T.; Downard, A.; Parvez, M. Inorg. Chem. 1999, 38, 4347.
(40) Bülow, R. v.; Gornitzka, H.; Kottke, T.; Stalke, D. J. Chem. Soc.,
molecules of 6 arranged in a column, with the interacting atoms Chem. Commun. 1996, 1639.
labeled (50% thermal ellipsoids). TMEDA and TMS methyl groups (41) Bülow, R. v.; Deuerlein, S.; Stey, T.; Herbst-Irmer, R.; Gornitzka,
and all noninteracting hydrogen atoms are omitted for clarity. H.; Stalke, D. Z. Naturforsch. 2004, 59b, 1471.
N,N′-Bis-Silylated Lithium Aryl Amidinates Organometallics, Vol. 27, No. 8, 2008 1875
Conclusions NMR (300 MHz, toluene-d8) δ 6.61–6.50 (m, 4H, Ph), 2.83 (q, 3J
) 3.9 Hz, 2H, CH2-Ph), 2.04 (s, 12H, CH3N), 1.85 (s, 4H, CH2N),
Nine new lithium amidinate complexes were synthesized and 1.44 (t, 3J ) 3.9 Hz, 3H, CH2CH3), 0.22 (s, 18H, CH3Si); 13C
characterized. The dimeric lithium bis(trimethylsilyl) amide NMR (300 MHz, toluene-d8) δ 178.1 (N-C-N), 147.6, 129.3,
2-ethyl benzonitrilenitrile adduct was identified as a kinetically 128.4, 127.0, 126.3, 126.0 (Ph), 56.4 (CH2N), 45.6 (CH3N), 25.8
stable intermediate in the formation of the amidinate. We have (CH2-Ph), 14.1 (CH2CH3), 6.6 (CH3Si). Anal. Calcd for C21H43-
found that the amidinate complexes are differentiated by the LiN4Si2 (414.70): C, 60.82; H, 10.45; N, 13.51. Found: C, 55.91;
involvement degree of their π system in bonding to lithium, H, 10.14; N, 12.44.
manifested in its deviation from the NCN plane. This involve- [p-EtC6H4C(NSiMe3)2]Li · TMEDA (2). A 2.15 g (16.4 mmol)
ment, which comes at the expanse of the N-Li σ bonds, is sample of p-ethylbenzonitrile gave 5.43 g (80% yield) of 2. 1H
caused by the relatively weak crystalline packing forces. The NMR (300 MHz, toluene-d8) δ 7.28 (d, 3J ) 9.0 Hz, 2H, Ph), 7.04
substantial changes to the amidinate coordination mode inflicted (d, 3J ) 6.0 Hz, 2H, Ph), 2.52 (q, 3J ) 6.0 Hz, 2H, CH2-Ph), 2.08
by these different supramolecular arrangements and the existence (s, 12H, CH3N), 1.89 (s, 4H, CH2N), 1.16 (t, 3J ) 6.0 Hz, 3H,
of aggregates that contain lithium amidinates and metal salts CH2CH3), 0.06 (s, 18H, CH3Si); 13C NMR (300 MHz, toluene-d8)
indicate the plausible role of the amidinate π system in ligand δ 179.9 (N-C-N), 145.7, 141.5, 126.8, 126.2 (Ph), 56.4 (CH2N),
metathesis reactions. 45.6 (CH3N), 28.9(CH2-Ph), 16.0 (CH2CH3), 3.3 (CH3Si). Anal.
Calcd for C21H43LiN4Si2 (414.70): C, 60.82; H, 10.45; N, 13.51.
Experimental Section Found: C, 58.98; H, 10.24; N, 13.51.
General Procedure. All manipulations of air-sensitive materials [p-nBuC6H4C(NSiMe3)2]Li · TMEDA (3). A 2.55 g (16.0 mmol)
were carried out with the vigorous exclusion of oxygen and moisture sample of p-n-butylbenzonitrile gave 6.24 g (88% yield) of 3. 1H
in oven-dried or flamed Schlenk-type glassware on a dual-manifold NMR (300 MHz, toluene-d8) δ 7.23 (d, 3J ) 9.0 Hz, 2H, Ph), 7.00
Schlenk line, or interfaced to a high-vacuum (10–5 Torr) line, or in (d, 3J ) 9.0 Hz, 2H, Ph), 2.46 (t, 3J ) 6.0 Hz, 2H, CH2-Ph), 2.03
a nitrogen-filled Vacuum Atmospheres glovebox with a medium- (s, 12H, CH3N), 1.84 (s, 4H, CH2N), 1.50 (quintet, 3J ) 6.0 Hz,
capacity recirculator (1–2 ppm O2). Argon and nitrogen were 2H, CH3CH2CH2CH2-Ph), 1.28 (sextet, 3J ) 6.0 Hz, 2H, CH3CH2-
purified by passage through a MnO oxygen-removal column and a CH2CH2-Ph), 0.86 (t, 3J ) 6.0 Hz, 3H, CH3CH2CH2CH2-Ph), 0.05
Davison 4 Å molecular sieve column. Hexane, ether, and toluene- (s, 18H, CH3Si);13C NMR (500 MHz, toluene-d8) δ 180.2 (N-C-N),
d8 were distilled under nitrogen from Na-K alloy. TMEDA and 145.8, 140.3, 127.6, 126.3 (Ph), 56.5 (CH2N), 45.6 (CH3N), 35.8 (CH2-
toluene were distilled under nitrogen from Na. 2-Furonitrile was Ph), 34.1 (CH3CH2CH2CH2-Ph), 22.6 (CH3CH2CH2CH2-Ph), 14.1
dried overnight with CaO and distilled at room temperature under (CH3CH2CH2CH2-Ph), 3.4 (CH3Si). Anal. Calcd for C23H47LiN4Si2
reduced pressure. Lithium bis(trimethylsilyl) amide, benzonitriles, (442.76): C, 62.39; H, 10.70; N, 12.65. Found: C, 57.17; H, 10.24;
2-cyanopyridine, and 2-furaldehyde were purchased from Aldrich N, 11.70.
and used as received. 1H and 13C spectra were recorded on Bruker [p-tBuC6H4C(NSiMe3)2]Li · TMEDA (4). A 2.55 g (16.0 mmol)
Avance 300 and 500 spectrometers. 1H and 13C Chemical shifts sample of p-tert-butylbenzonitrile gave 6.38 g (90% yield) of 4.
are referenced to internal solvent resonances and reported relative 1
H NMR (500 MHz, toluene-d8) δ 7.23 (dd, 3J ) 8.5 Hz, 1.1 Hz,
to tetramethylsilane. The experiments were conducted in Teflon- 2H, Ph), 7.26 (dd, 3J ) 8.5 Hz, 1.1 Hz, 2H, Ph), 2.03 (s, 12H,
sealed NMR tubes (J. Young) after preparation of the sample under CH3N), 1.84 (s, 4H, CH2N), 1.23 (s, 9H, CH3), 0.04 (s, 18H,
anaerobic conditions, with dried toluene-d8. CH3Si); 13C NMR (500 MHz, toluene-d8) δ 180.2 (N-C-N),
X-ray Diffraction Spectroscopy. Single crystals immersed in 148.8, 145.5, 126, 124.3 (Ph), 56.5 (CH2N), 45.6 (CH3N), 34.4
dry and degassed Paraton-N oil were quickly fished with a glass (CMe3), 31.6 (CH3), 3.4 (CH3Si). Anal. Calcd for C23H47LiN4Si2
rod and mounted on a KappaCCD diffractometer under a cold (442.76): C, 62.39; H, 10.70; N, 12.65. Found: C, 59.04; H, 11.51;
stream of nitrogen at 230 K. Data collection and processing and N, 12.27.
structure solving were carried out with use of previously reported [p-MeOC6H4C(NSiMe3)2]Li · TMEDA (5). A 2.20 g (16.5
equipment and techniques.6 mmol) sample of p-methoxybenzonitrile gave 6.13 g (89% yield)
Syntheses. Synthesis of 2-Furonitrile. 2-Furonitrile was syn- of 5. 1H NMR (300 MHz, toluene-d8) δ 7.28 (d, 3J ) 9.0 Hz, 2H,
thesized in high yield from 2-furaldehyde with a published method49 Ph), 7.04 (d, 3J ) 6.0 Hz, 2H, Ph), 3.23 (s, 3H, CH3-O), 1.95 (s,
and was dried and purified as described above. 12H, CH3N), 1.75 (s, 4H, CH2N), 0.03 (s, 18H, CH3Si); 13C NMR
Typical Procedure for Syntheses of Complexes 1–8. A frit
(200 MHz, toluene-d8) δ 179.9 (N-C-N), 158.4, 141.2, 127.4,
equipped with two 100 mL flasks was charged with lithium
112.9 (Ph), 56.4 (CH2N), 54.5 (CH3-O), 45.6 (CH3N), 3.5 (CH3Si).
bis(trimethylsilyl) amide (16.0–16.8 mmol) inside the glovebox.
Anal. Calcd for C20H41LiN4OSi2 (416.68): C, 57.65; H, 9.92; N,
The frit was then connected to a high-vacuum line and the solids
13.45. Found: C, 53.62; H, 9.33; N, 12.67.
were dissolved in 30 mL of hexane. The resulted solution was
[m-MeOC6H4C(NSiMe3)2]Li · TMEDA (6). A 2.20 g (16.5
cooled to 0 °C and an equimolar amount of the nitrile was added
dropwise with a syringe. p-Methoxybenzonitrile was melted and mmol) sample of o-methoxybenzonitrile gave 4.82 g (70% yield)
injected with a heated syringe, resulting in the formation of solids of 6. 1H NMR (300 MHz, toluene-d8) δ 7.06 (t, 3J ) 9.0 Hz, 1H,
(except for 8). The cooling bath was removed and the mixture was Ph), 6.88 (m, 2H, Ph), 7.06 (dd, 1H, Ph), 3.40 (s, 3H, CH3-O),
kept stirring at room temperature for 3 h. TMEDA (1.5 equiv) was 2.02 (s, 12H, CH3N), 1.82 (s, 4H, CH2N), 0.04 (s, 18H, CH3Si);
13
then added, giving an almost clear solution, which was stirred for C NMR (500 MHz, toluene-d8) δ 179.3 (N-C-N), 159.5, 149.4,
an additional 3 h and filtered to remove solid impurities. Volatiles 128.6, 118.9, 112.0, 111.9 (Ph), 56.4 (CH2N), 54.5 (CH3-O), 45.6
were gradually evaporated from the filtrate until precipitation started, (CH3N), 3.3 (CH3Si). Anal. Calcd for C20H41LiN4OSi2 (416.68):
and the concentrated solution was kept at -40 °C overnight to yield C, 57.65; H, 9.92; N, 13.45. Found: C, 54.40; H, 9.46; N, 13.05.
crystals of the product. Repetition of the crystallization process gave [o-MeOC6H4C(NSiMe3)2]Li · TMEDA (7). A 2.20 g (16.5
an additional crop of crystals. mmol) sample of o-methoxybenzonitrile gave 5.85 g (85% yield)
[o-EtC6H4C(NSiMe3)2]Li · TMEDA (1). A 2.15 g (16.4 mmol)- of 7. 1H NMR (300 MHz, toluene-d8) δ 7.08 (dd, 3J ) 9.0 Hz,
sample of o-ethylbenzonitrile gave 5.09 g (75% yield) of 1. 1H 1H, Ph), 6.95 (t, 3J ) 9.0 Hz, 1H, Ph), 6.75 (t, 3J ) 9.0 Hz, 1H,
Ph), 6.46 (dd, 3J ) 9.0 Hz, 1H, Ph), 3.34 (s, 3H, CH3-O), 1.96 (s,
(49) Talukdar, S.; Hsu, J. L.; Chou, T. C.; Fang, J. M. Tetrahedron 12H, CH3N), 1.78 (s, 4H, CH2N), -0.03 (s, 18H, CH3Si); 13C NMR
Lett. 2001, 42, 1103. (500 MHz, toluene-d8) δ 175.6 (N-C-N), 154.6, 133.7, 128.1,
N,N′-Bis-Silylated Lithium Aryl Amidinates Organometallics, Vol. 27, No. 8, 2008 1877
127.0, 119.8, 110.0 (Ph), 56.5 (CH2N), 53.8 (CH3-O), 45.6 (CH3N), C18H38LiN5Si2 (387.64): C, 55.77; H, 9.88; N, 18.07. Found: C,
2.9 (CH3Si). Anal. Calcd for C20H41LiN4OSi2 (416.68): C, 57.65; 52.99; H, 9.95; N, 17.28.
H, 9.92; N, 13.45. Found: C, 53.86; H, 9.48; N, 12.34. {[N(SiMe3)2]Li · o-EtC6H4CN}2 (10). A 826 mg (4.9 mmol)
[2-C4H3OC(NSiMe3)2]Li · TMEDA (8). A 1.56 g (16.8 mmol) sample of lithium bis(trimethylsilyl) amide were charged in the
sample of 2-furonitrile gave 5.24 g (83% yield) of 8. 1H NMR glovebox into a frit equipped with two 50 mL flasks. The frit was
(300 MHz, toluene-d8) δ 6.96 (dd, 3J ) 1.7 Hz, 0.6 Hz, 1H, furyl), connected to a high-vacuum line and 20 mL of ether was added.
6.10 (d, 3J ) 2.9 Hz, 1H, furyl), 6.03 (dd, 3J ) 2.9 Hz, 1.7 Hz, The resulting slurry was cooled to 0 °C and a solution of 647 mg
1H, furyl), 1.90 (s, 12H, CH3N), 1.73 (s, 4H, CH2N), 0.03 (s, 18H, (4.9 mmol) of the nitrile in 4 mL of hexane was added dropwise
CH3Si); 13C NMR (300 MHz, toluene-d8) δ 167.9 (N-C-N), 156, with a syringe. The cooling bath was removed and the mixture
was stirred at room temperature for 10 min, after which a clear
138.7, 110.3, 105.0 (furyl), 56.4 (CH2N), 45.5 (CH3N), 3.3 (CH3Si).
solution was obtained. Colorless crystals (1.20 g, 81% yield) of
Anal. Calcd for C17H37LiN4OSi2 (376.61): C, 54.22; H, 9.90; N,
the product were obtained by gradual evaporation of the solvents.
14.88. Found: C, 52.29; H, 9.73; N, 13.77. 1
H NMR (300 MHz, toluene-d8) δ 7.11 (dd, 3J ) 7.8 Hz, 1.2 Hz,
[2-C5H4NC(NSiMe3)2]Li · TMEDA (9). A frit equipped with two 2H, Ph), 6.88 (dt, 3J ) 7.8 Hz, 1.2 Hz, 2H, Ph) 6.65 (d, 3J ) 7.5
100 mL flasks was charged with 2.81 g (16.8 mmol) of lithium Hz, 2H, Ph) 6.59 (dt, 3J ) 7.8 Hz, 1.2 Hz, 2H, Ph) 2.56 (q, 3J )
bis(trimethylsilyl) amide inside the glovebox. Fifteen milliliters of 7.5 Hz, 4H, CH2-Ph), 1.04 (t, 3J ) 7.5 Hz, 6H, CH2CH3), 0.51 (s,
hexane and 15 mL of TMEDA were injected to the frit, and the 36H, CH3Si); 13C NMR (300 MHz, toluene-d8) δ 148.7 (C-Et),
resulting solution was cooled to 0 °C. Melted 2-cyanopyridine (1.75 133.4, 133.0, 126.4 (C-H, Ph), 118.6 (CN), 110.7 (C-CN),
g, 16.8 mmol) was then injected, resulting in an almost clear yellow 27.8(CH2-Ph), 15.1 (CH2CH3), 6.3 (CH3Si). Anal. Calcd for
solution. The cooling bath was removed and the solution was kept C30H54Li2N4Si4 (597.00): C, 60.36; H, 9.12; N, 9.38. Found: C,
stirring at room temperature for 3 h, and then filtered to remove 55.09; H, 8.36; N, 8.12.
solid impurities. Solvents were gradually removed from the filtrate
until precipitation started, and the concentrated solution was kept Acknowledgment. This research was supported by the
at -40 °C overnight to yield yellow-brown crystals of the product USA-Israel Binational Science Foundation under contract
(4.04 g, 62% yield). 1H NMR (300 MHz, toluene-d8) δ 8.26 (s, br, 2004075.
1H, H-CdN), 6.90–7.60 (s, br, 1H, pyridyl), 7.13 (t, 3J ) 6.9 Hz,
1H, pyridyl), 6.68 (ddd, 3J ) 8.7 Hz, 4.8 Hz, 1.8 Hz, 1H, pyridyl), Supporting Information Available: Crystallographic data for
complexes 1–10 are available in CIF format. This material is
1.96 (s, 12H, CH3N), 1.81 (s, 4H, CH2N), 0.153 (s, 18H, CH3Si);
13 available free of charge via the Internet at http://pubs.acs.org.
C NMR (300 MHz, toluene-d8) δ 148.2, 135.3, 121.3 (pyridyl),
56.5 (CH2N), 45.6 (CH3N), 3.3 (CH3Si). Anal. Calcd for OM701216P