Group 13 and 14 alkyl derivatives of the imido-nitrido metalloligand [{Ti(η5-C5Me5)(μ-NH)} 3(μ3-N)]

Article abstract of DOI:10.1021/om060895+

The reactivity of the imido-nitrido trinuclear complex [{Ti- (η⁵-C₅Me₅)(μ-NH)}₃(μ ₃-N)] (1) toward alkyl derivatives of group 13 and 14 elements has been investigated. Treatment of 1 with trialkyl der

Full text of DOI:10.1021/om060895+

4
08
Organometallics 2007, 26, 408-416
Group 13 and 14 Alkyl Derivatives of the Imido-Nitrido
5
Metalloligand [{Ti(η -C Me )(µ-NH)} (µ -N)]
5
5
3
3
Mar ´ı a Garc ´ı a-Castro, Avelino Mart ´ı n, Miguel Mena, and Carlos Y e´ lamos*
Departamento de Qu ´ı mica Inorg a´ nica, UniVersidad de Alcal a´ , 28871 Alcal a´ de Henares, Madrid, Spain
ReceiVed September 29, 2006
5
The reactivity of the imido-nitrido trinuclear complex [{Ti(η -C
5
Me
5
)(µ-NH)}
3
3
(µ -N)] (1) toward
alkyl derivatives of group 13 and 14 elements has been investigated. Treatment of 1 with trialkyl derivatives
5
of aluminum, gallium, or indium at room temperature afforded the adducts [R
Me (µ -N)}] (R ) CH SiMe , M ) Al (3), Ga (4), In (5); R ) CH , M ) Ga (6), In (7)). The
analogous reaction of 1 with [AlMe ] at 90 °C gave the methylaluminum derivative [MeAl{(µ -N) (µ
-N)}] (8) via methane elimination. Complexes 3 and 6 at this temperature gave
3
M{(µ
3
-NH)
3
Ti
3
(η -C
5
-
5
)
3
3
2
3
2 6 5
C H
3
3
2
3
-
5
NH)Ti
also monoalkyl complexes [RM{(µ
M ) Ga, R ) CH (11)), whereas the indium derivative 7 led to the indium(I) complex [In{(µ
(µ -N)}] (12) and bibenzyl. Analogous chloromethylaluminum adducts [Me
Me (µ
3
(η -C
5
Me
5
)
3
(µ
3
5
3
-N)
2
(µ
3
-NH)Ti
3
(η -C
5
Me
5
)
3
(µ
3
2 3
-N)}] (M ) Al, R ) CH SiMe (9);
2
C
6
H
5
3
-
-
5
N)(µ
3
-NH)
Cl3-nAl{(µ
AlCl3-nMe
2
Ti
3
(η -C
Ti
5
Me
5
)
3
3
n
5
3
-NH)
3
3
(η -C
5
5
)
3
3
-N)}] (n ) 1 (13), 2 (14)) were obtained by treatment of 1 with
5
[
n
]. Reaction of the lithium reagent [Li(µ
germanium, and silicon chloroalkyl derivatives [MClMe
4
-N)(µ
] gave the group 14 alkyl complexes [Me
-N)}] (M ) Sn (15), Ge (16), Si (17)). The X-ray crystal structures of
3
-NH)
2
{Ti
3
(η -C
5
Me
5
)
3
(µ
3
-N)}]
2
with tin,
3
3
M-
5
{
6
(µ
3
-N)Ti
3
(η -C
5
Me
5
)
3
(µ-NH)
2
(µ
3
, 7, 9, 13, 15, and 16 have been determined.
Introduction
The chemistry of trialkyl derivatives of group 13 with
macrocyclic amines is comparatively scarcer. Several examples
show the formation of adducts with macrocyclic amines, but
The reactions of trialkyl derivatives of group 13 elements
6
1
(
M ) Al, Ga, In) with amines have been studied for decades.
at high temperatures the derivatives containing macrocyclic
Trialkylmetal-amine adducts [R3M(NR′3)] are formed in the
7
secondary amines release alkanes. As an exception, the 1:1
2
first step of the reaction. In many cases, adducts with secondary
adduct [AlMe3{(tacn)H}] ((tacn)H ) 1,4-diisopropyl-1,4,7-
or primary amines [R3M(NHR′2)] decompose at moderate
temperatures via alkane RH elimination to give amido com-
plexes [{R2M(NR′2)}n], the most common in the literature being
the dimeric structures containing a four-membered ring with
triazacyclononane) is surprisingly thermally stable and does not
8
release methane in refluxing toluene. Most of those examples
(4) (a) Uhl, W.; Roesky, H. W. In Molecular Clusters of the Main Group
Elements; Driess, M., N o¨ th, H., Eds.; Wiley-VCH: Weinheim, Germany,
3
alternating metal and nitrogen atoms. Further heating at higher
2
2
004; pp 357-390. (b) Timoshkin, A. Y. Coord. Chem. ReV. 2005, 249,
temperatures of the amido derivatives obtained from primary
amines [{R2M(NHR′)}n] may result in an additional alkane
elimination with formation of more condensed imido species
094-2131.
(5) For selected examples, see: (a) Amirkhalili, S.; Hitchcock, P. B.;
Smith, J. D. J. Chem. Soc., Dalton Trans. 1979, 1206-1212. (b) Waggoner,
K. M.; Hope, H.; Power, P. P. Angew. Chem., Int. Ed. Engl. 1988, 27,
4
,5
[
{RM(NR′)}n].
1
699-1700. (c) Waggoner, K. M.; Power, P. P. J. Am. Chem. Soc. 1991,
113, 3385-3393. (d) Belgardt, T.; Roesky, H. W.; Noltemeyer, M.; Schmidt,
*
Corresponding author. Fax: (+34) 91-8854683. E-mail: carlos.yelamos@
H.-G. Angew. Chem., Int. Ed. Engl. 1993, 32, 1056-1058. (e) Schnitter,
C.; Waezsada, S. D.; Roesky, H. W.; Teichert, M.; Us o´ n, I.; Parisini, E.
Organometallics 1997, 16, 1197-1202. (f) Styron, E. K.; Lake, C. H.;
Powell, D. H.; Krannich, L. K.; Watkins, C. L. J. Organomet. Chem. 2002,
649, 78-85.
uah.es.
(
1) For pioneering work, see: (a) Robinson, G. H. In ComprehensiVe
Coordination Chemistry II; Parkin, G. F. R., McCleverty, J. A., Meyer, T.
J., Eds.; Elsevier: Oxford, UK, 2004; Vol. 3, pp 347-382. (b) Coates, G.
E.; Whitcombe, R. A. J. Chem. Soc. 1956, 3351-3354. (c) Laubengayer,
A. W.; Smith, J. D.; Ehrlich, G. G. J. Am. Chem. Soc. 1961, 83, 542-546.
(6) (a) Robinson, G. H.; Zhang, H.; Atwood, J. L. J. Organomet. Chem.
1987, 331, 153-160. (b) Robinson, G. H.; Pennington, W. T.; Lee, B.;
Self, M. F.; Hrncir, D. C. Inorg. Chem. 1991, 30, 809-812. (c) Bradley,
D. C.; Frigo, D. M.; Harding, I. S.; Hursthouse, M. B.; Motevalli, M. J.
Chem. Soc., Chem. Commun. 1992, 577-578. (d) Coward, K. M.; Jones,
A. C.; Steiner, A.; Bickley, J. F.; Smith, L. M.; Pemble, M. E. J. Chem.
Soc., Dalton Trans. 2001, 41-45.
(7) (a) Robinson, G. H.; Rae, A. D.; Campana, C. F.; Byram, S. K.
Organometallics 1987, 6, 1227-1230. (b) Robinson, G. H.; Appel, E. S.;
Sangokoya, S. A.; Zhang, H.; Atwood, J. L. J. Coord. Chem. 1988, 17,
373-379. (c) Robinson, G. H.; Self, M. F.; Sangokoya, S. A.; Pennington,
W. T. J. Am. Chem. Soc. 1989, 111, 1520-1522. (d) Lee, B.; Pennington,
W. T.; Robinson, G. H.; Rogers, R. D. J. Organomet. Chem. 1990, 396,
269-278. (e) Lee, B.; Pennington, W. T.; Robinson, G. H. Organometallics
1990, 9, 1709-1711. (f) Pajerski, A. D.; Cleary, T. P.; Parvez, M.; Gokel,
G. W.; Richey, H. G., Jr. Organometallics 1992, 11, 1400-1402. (g)
Robson, D. A.; Bylikin, S. Y.; Cantuel, M.; Male, N. A. H.; Rees, L. H.;
Mountford, P.; Schr o¨ der, M. J. Chem. Soc., Dalton Trans. 2001, 157-
169.
(
2) For representative examples, see: (a) Bradley, D. C.; Dawes, H. M.;
Hursthouse, M. B.; Smith, L. M.; Thornton-Pett, M. Polyhedron 1990, 9,
43-351. (b) Atwood, D. A.; Jones, R. A.; Cowley, A. H.; Bott, S. G.;
3
Atwood, J. L. Polyhedron 1991, 10, 1897-1902. (c) Thomas, C. J.;
Krannich, L. K.; Watkins, C. L. Polyhedron 1993, 12, 389-399. (d) Schauer,
S. J.; Watkins, C. L.; Krannich, L. K.; Gala, R. B.; Gundy, E. M.; Lagrone,
C. B. Polyhedron 1995, 14, 3505-3514. (e) Bradley, D. C.; Coumbarides,
G.; Harding, I. S.; Hawkes, G. E.; Maia, I. A.; Motevalli, M. J. Chem.
Soc., Dalton Trans. 1999, 3553-3558.
(
3) For examples, see: (a) Byers, J. J.; Lee, B.; Pennington, W. T.;
Robinson, G. H. Polyhedron 1992, 11, 967-972. (b) Schauer, S. J.;
Pennington, W. T.; Robinson, G. H. Organometallics 1992, 11, 3287-
3
292. (c) Schauer, S. J.; Lake, C. H.; Watkins, C. L.; Krannich, L. K.
Organometallics 1996, 15, 5641-5644. (d) Schauer, S. J.; Lake, C. H.;
Watkins, C. L.; Krannich, L. K.; Powell, D. H. J. Organomet. Chem. 1997,
5
49, 31-37. (e) Styron, E. K.; Lake, C. H.; Watkins, C. L.; Krannich, L.
K. Organometallics 1998, 17, 4319-4321. (f) Styron, E. K.; Lake, C. H.;
Schauer, S. J.; Watkins, C. L.; Krannich, L. K. Polyhedron 1999, 18, 1595-
(8) Cui, C.; Giesbrecht, G. R.; Schmidt, J. A. R.; Arnold, J. Inorg. Chim.
Acta 2003, 351, 404-408.
1
602.
1
0.1021/om060895+ CCC: $37.00 © 2007 American Chemical Society
Publication on Web 12/14/2006

5
Imido-Nitrido Metalloligand [{Ti(η -C
5
Me
5
)(µ-NH)}
3
(µ
3
-N)]
Organometallics, Vol. 26, No. 2, 2007 409
5
show the coordination of the macrocyclic nitrogen donors to
several alkylmetal fragments, while their link as chelate to a
single alkyl group 13 metal center remains rare. Early work by
Ito and co-workers demonstrated the formation of the complex
Scheme 1. Reactions of 1 with [MR
3
] ([Ti] ) Ti(η -C
5
Me
5
))
[AlEtL] by reaction of [AlEt3] in hexane solution with the
macrocyclic H2L (L ) [C22H24N4]) via a two-step ethane
9
elimination sequence. Similar complexes [MRL] and [MR2L]
were characterized later from the reactions of aluminum,
gallium, and indium trialkyl derivatives with analogous poly-
dentate amines.10
In the last few years, we have been studying the coordination
chemistry of the trinuclear titanium imido-nitrido complex [{Ti-
1
8
19
5
11,12
2 3 3
silylmethyl) derivatives [M(CH SiMe ) ] of aluminum, gallium,
(
η -C5Me5)(µ-NH)}3(µ3-N)]
(1). Compound 1 shows a cyclic
20
or indium in hexane at room temperature led to the precipita-
tion of the group 13 adducts [(Me3SiCH2)3M{(µ3-NH)3Ti3(η -
C5Me5)3(µ3-N)}] (M ) Al (3), Ga (4), In (5)) as yellow or
orange solids in 43-63% yields. Analogous reactions of 1 with
tribenzyl derivatives of gallium and indium [M(CH2C6H5)3(thf)x]
M ) Ga, x ) 1; M ) In, x ) 0) in toluene afforded the
adducts [(C6H5CH2)3M{(µ3-NH)3Ti3(η -C5Me5)3(µ3-N)}] (M )
Ga (6), In (7)) as orange crystals in 51-59% yield.
[Ti3(µ-NH)3] system with three NH electron-donor imido groups
5
similar to the macrocyclic secondary triamines. Our previous
work with transition metal derivatives has shown that 1 is
capable of acting as a neutral tridentate ligand through the basal
NH groups, but later those imido groups can also be deproto-
nated to give monoanionic, dianionic, and even trianionic forms
of 1 depending on the metal and the other ligands present in
2
1
22
(
5
the coordination sphere.1
3,14
More recently, we have also
demonstrated the ability of 1 to coordinate main-group metal
cyclopentadienides and halides to give the adducts [XnM{(µ3-
The trimethylsilylmethyl derivatives 3-5 are light sensitive
in solution, giving unknown greenish products, and therefore
their preparations and manipulations in solution were carried
out in amber-colored flasks. Solutions of the benzyl derivatives
6 and 7 were not altered under ambient light during weeks in
an argon atmosphere. Compounds 3-7 were characterized by
spectral and analytical methods, as well as by X-ray crystal
structure determinations for 6 and 7. The mass spectra of
complexes 3-7 (EI, 70 eV) do not show the expected molecular
peaks for the adducts, but those found of higher mass/charge
correspond to the elimination of alkyl groups from the mol-
ecules. IR spectra (KBr) of complexes 3-7 reveal one νNH
5
15
NH)3Ti3(η -C5Me5)3(µ3-N)}]. Additionally in this similarity
with amines, 1 can be deprotonated by treatment with lithium
bis(trimethylsilyl)amido to give the lithium complex [Li(µ4-N)-
5
16,17
(
µ3-NH)2{Ti3(η -C5Me5)3(µ3-N)}]2 (2),
which has shown to
be an efficient reagent to prepare new heterometallic nitrido
1
4,16
complexes through the reaction with chloride derivatives.
Herein, we report the synthesis, structure, and thermal
behavior of adducts of 1 with group 13 alkyl derivatives. The
analogous reactions of 1 with group 14 alkyl derivatives were
not successful, but several compounds were obtained through
the metathesis reaction of 2 with group 14 cloroalkyl derivatives.
-
1
vibration in the range 3361-3343 cm similar to the value
-1
determined for 1, 3352 cm , and other adducts of 1 with metal
15
1
13
cyclopentadienides and halides. The H and C NMR spectra
in benzene-d6 or chloroform-d1 at room temperature of com-
plexes 3, 6, and 7 show resonances for equivalent NH, C5Me5,
and alkyl groups, suggesting a highly symmetrical structure or
the existence of dynamic exchange processes with a low-energy
barrier in solution, in a similar fashion to those found in the
Results and Discussion
Reactions with Group 13 Trialkyl Derivatives. The syn-
thetic chemistry is outlined in Scheme 1. Treatment of [{Ti-
5
(
η -C5Me5)(µ-NH)}3(µ3-N)] (1) with 1 equiv of tris(trimethyl-
5
analogous compounds [I3In{(µ3-NH)3Ti3(η -C5Me5)3(µ3-N)}]
5
15b
(
9) Goedken, V. L.; Ito, H.; Ito, T. J. Chem. Soc., Chem. Commun. 1984,
453-1454.
10) (a) Alcock, N. W.; Blacker, N. C.; Wallbridge, M. G. H.; Barker,
and [Cl2Sn{(µ3-NH)3Ti3(η -C5Me5)3(µ3-N)}]. The NH reso-
nance signals in these spectra (δ ) 12.7-12.4) are shifted to a
higher field than that found for 1 (δ ) 13.8). We have noted
1
(
J. J. Organomet. Chem. 1991, 419, C23-C26. (b) Alcock, N. W.; Blacker,
N. C.; Errington, W.; Wallbridge, M. G. H. Acta Crystallogr. C 1993, 49,
1
5
an analogous shift in other adducts of 1 and used those data
1
359-1361. (c) Cannadine, J. C.; Errington, W.; Moore, P.; Wallbridge,
M. G. H.; Nield, E.; Fenn, D. J. Organomet. Chem. 1995, 486, 237-242.
d) Phillips, P. R.; Wallbridge, M. G. H.; Barker, J. J. Organomet. Chem.
998, 550, 301-308.
11) Roesky, H. W.; Bai, Y.; Noltemeyer, M. Angew. Chem., Int. Ed.
Engl. 1989, 28, 754-755.
12) Abarca, A.; G o´ mez-Sal, P.; Mart ´ı n, A.; Mena, M.; Poblet, J.-M.;
Y e´ lamos, C. Inorg. Chem. 2000, 39, 642-651.
13) (a) Abarca, A.; Galakhov, M.; G o´ mez-Sal, P.; Mart ´ı n, A.; Mena,
M.; Poblet, J.-M.; Santamar ´ı a, C.; Sarasa, J. P. Angew. Chem., Int. Ed. 2000,
to propose the coordination of the NH groups to the incorporated
13
elements. C NMR spectra revealed a singlet for the ipso-carbon
resonance of the C5Me5 ligands (δ ) 120.3-120.0), which is
(
1
(
slightly shifted downfield with respect to that found for 1 (δ )
12
1
17.1).
(
Surprisingly, the trimethylsilylmethyl derivatives of gallium
(
4
and indium 5 are not soluble in benzene-d6 and decompose
in chloroform-d1, precluding their characterization by NMR
spectroscopy. However, NMR analysis of the dilute resultant
solutions in benzene-d6 reveals resonance signals almost identi-
3
9, 534-537. (b) Abarca, A.; Mart ´ı n, A.; Mena, M.; Y e´ lamos, C. Angew.
Chem., Int. Ed. 2000, 39, 3460-3463. (c) Abarca, A.; Galakhov, M. V.;
Gracia, J.; Mart ´ı n, A.; Mena, M.; Poblet, J.-M.; Sarasa, J. P.; Y e´ lamos, C.
Chem.-Eur. J. 2003, 9, 2337-2346.
(14) Freitag, K.; Gracia, J.; Mart ´ı n, A.; Mena, M.; Poblet, J.-M.; Sarasa,
J. P.; Y e´ lamos, C. Chem.-Eur. J. 2001, 7, 3644-3651.
(18) (a) Nyathi, J. Z.; Ressner, J. M.; Smith, J. D. J. Organomet. Chem.
1974, 70, 35-38. (b) Beachley, O. T., Jr.; Tessier-Youngs, C.; Simmons,
R. G.; Hallock, R. B. Inorg. Chem. 1982, 21, 1970-1973.
(19) Beachley, O. T., Jr.; Simmons, R. G. Inorg. Chem. 1980, 19, 1021-
1025.
(
15) (a) Garc ´ı a-Castro, M.; Mart ´ı n, A.; Mena, M.; Y e´ lamos, C. Orga-
nometallics 2004, 23, 1496-1500. (b) Garc ´ı a-Castro, M.; Gracia, J.; Mart ´ı n,
A.; Mena, M.; Poblet. J.-M.; Sarasa, J. P.; Y e´ lamos, C. Chem.-Eur. J.
2
005, 11, 1030-1041.
(
16) Garc ´ı a-Castro, M.; Mart ´ı n, A.; Mena, M.; P e´ rez-Redondo, A.;
Y e´ lamos, C. Chem.-Eur. J. 2001, 7, 647-651.
17) Mart ´ı n, A.; Mena, M.; P e´ rez-Redondo, A.; Y e´ lamos, C. Inorg. Chem.
004, 43, 2491-2498.
(20) Beachley, O. T., Jr.; Rusinko, R. N. Inorg. Chem. 1979, 18, 1966-
1968.
(
(21) Neum u¨ ller, B.; Gahlmann, F. Chem. Ber. 1993, 126, 1579-1585.
(22) Barron, A. R. J. Chem. Soc., Dalton Trans. 1989, 1625-1626.
2

4
10 Organometallics, Vol. 26, No. 2, 2007
Garc ´ı a-Castro et al.
of group 13 tribenzyl adducts [M(CH2C6H5)3(L)] (M ) Ga, In)
when compared with the analogous trimethylsilylmethyl deriva-
tives [M(CH2SiMe3)3(L)] has been observed previously and
attributed to the decreased steric bulk of the benzyl ligand.22
The molecular structures of complexes 6 and 7 are presented
in Figures 1 and 2, and selected distances and angles for both
compounds are given in Table 1. The solid-state structures show
a distorted tetrahedral geometry for the gallium and indium
centers, comprising three methylene carbon atoms of the benzyl
groups and one nitrogen atom of the metalloligand 1. The benzyl
groups stay in a propeller-like disposition like that shown by
2
1
the starting reagent [Ga(CH2C6H5)3(thf)]. The gallium-
nitrogen, 2.094(2) Å, and gallium-carbon, average 2.036(3) Å,
bond lengths in 6 compare well with those found in other
2
5,26
trialkylgallium amine adducts.
(
The indium-nitrogen, 2.296-
2) Å, and indium-carbon bond lengths in 7, average 2.248(3)
Å, are similar to other trialkylindium amine adducts.
26,27
Figure 1. Perspective view of 6 with thermal ellipsoids at the 50%
probability level.
The overall structure of 7 resembles that of the indium(III)
5
iodide adduct [I3In{(µ3-NH)3Ti3(η -C5Me5)3(µ3-N)}] reported
1
5b
by us. However, the higher electronic deficiency of indium
in the InI3 fragment makes shorter the In-N bond length (0.1
Å) and forces it to occupy the cavity formed in the inner part
of the metalloligand 1 to permit some interaction with the other
two imido groups, showing a value for the angle formed by the
In(1)-N(12) bond and the Ti(1)-Ti(2)-Ti(3) plane of 71.0-
(
3)°, while a value of 87.2(1)° is obtained for 7.
As can be seen in Table 1, the indium-nitrogen and indium-
carbon bond lengths in 7 are 0.202 and 0.212 Å longer than
the respective gallium bond lengths in 6, which correspond
mainly to the difference in covalent radii from gallium to indium
2
8
(
0.18 Å). The geometry about N(12) in both structures, sum
of angles M-N(12)-M ) 331.7° (6) and 326.8° (7), is close
to that expected for the ideal tetrahedral 328.5°. Within the
organometallic ligand the coordination of one NH group to gal-
lium or indium atoms does not affect significantly the average
bond distances and angles, presenting values close to those found
Figure 2. Perspective view of 7 with thermal ellipsoids at the 50%
probability level.
1
1
for the parent compound 1, except those related with the
nitrogen atom N(12) coordinated to the metal, which presents
longer Ti-N bonds (0.1 Å) and a narrower Ti-N(12)-Ti angle
Table 1. Selected Lengths (Å) and Angles (deg) for
Complexes 6 and 7
(4°).
M ) Ga (6)
M ) In (7)
In a procedure similar to the preparation of complexes 3-7,
M-N(12)
2.094(2)
2.036(3)
2.826(7)
1.920(2)
2.022(2)
1.917(2)
105.9(1)
112.8(1)
123.3(1)
118.9(1)
89.5(1)
2.296(2)
2.248(3)
2.821(1)
1.923(2)
2.004(3)
1.919(3)
105.9(1)
112.7(2)
119.6(1)
116.9(1)
90.3(1)
the reaction of 1 with trimethylaluminum in toluene at room
temperature gave an orange solution. Analysis by NMR
spectroscopy of the solution components revealed a mixture of
compounds containing Al-Me fragments. The reaction in
a
M-C
a
Ti‚‚‚Ti
a
Ti-N(1)
a
Ti-N(12)
a
1
Ti-(µ2-NH)
benzene-d6 was monitored by H NMR spectroscopy using an
a
N(12)-M-C
amber-colored NMR tube. The spectra at room temperature and
different reaction intervals showed resonances for several
organometallic species and methane. After heating at 90 °C for
4 days the spectra showed complete transformation of the
a
C-M-C
M-N(12)-Ti(1)
M-N(12)-Ti(2)
Ti(1)-N(12)-Ti(2)
a
Ti-(µ2-NH)-Ti
94.5(1)
94.8(1)
85.9(1)
106.9(1)
94.1(1)
94.4(1)
86.1(1)
106.4(1)
mixture to give resonance signals assigned to the complex
a
Ti-N(1)-Ti
5
[
MeAl{(µ3-N)2(µ3-NH)Ti3(η -C5Me5)3(µ3-N)}] (8) and methane
a
N(1)-Ti-Nimido
Nimido-Ti-Nimidoa
as the sole diamagnetic species in solution. In a preparative
experiment using amber-colored glassware, the reaction of 1
with [AlMe3] in hexane at 90 °C for 4 days afforded a red
solid. Analysis of this solid by NMR spectroscopy showed
a
Averaged values
cal to those determined for 1 and uncomplexed [M(CH2SiMe3)3]
reagents, suggesting the dissociation of complexes 4 and 5 in
solution. Partial dissociation in solution has been reported for
the complexes [(Me3SiCH2)3Ga{N(Me)2C2H4(Me)2N}Ga(CH2-
(25) (a) Krause, H.; Sille, K.; Hausen, H.-D.; Weidlein, J. J. Organomet.
Chem. 1982, 235, 253-264. (b) Obrey, S. J.; Bott, S. G.; Barron, A. R. J.
Organomet. Chem. 2002, 643-644, 53-60.
23
24
SiMe3)3] and [(Me3SiCH2)3Ga(PHPh2)]. The higher stability
(26) Lake, C. H.; Schauer, S. J.; Krannich, L. K.; Watkins, C. L.
Polyhedron 1999, 18, 879-883, and references therein.
(27) Bradley, D. C.; Dawes, H.; Frigo, D. M.; Hursthouse, M. B.;
Hussain, B. J. Organomet. Chem. 1987, 325, 55-67.
(28) Wiberg, N., Ed. Holleman-Wiberg Inorganic Chemistry, 1st English
ed.; Academic Press: New York, 2001; pp 1756-1759.
(
23) Hallock, R. B.; Hunter, W. E.; Atwood, J. L.; Beachley, O. T., Jr.
Organometallics 1985, 4, 547-549.
24) Banks, M. A.; Beachley, O. T., Jr.; Maloney, J. D.; Rogers, R. D.
Polyhedron 1990, 9, 335-342.
(

5
Imido-Nitrido Metalloligand [{Ti(η -C
5
Me
5
)(µ-NH)}
3
(µ
3
-N)]
Organometallics, Vol. 26, No. 2, 2007 411
Scheme 2. Thermal Behavior of Adducts
5
5
[R M{(µ
3
3
-NH)
3
Ti
3
(η -C
5
Me
5
)
3
(µ
3
5 5
-N)}] ([Ti] ) Ti(η -C Me ))
Figure 3. Perspective view of 9 with thermal ellipsoids at the 50%
probability level.
Table 2. Selected Lengths (Å) and Angles (deg) for 9
Al(1)-C(1)
1.946(8)
1.981(6)
1.929(5)
2.714(3)
90.6(2)
90.2(2)
127.9(4)
86.8(2)
93.2(2)
Al(1)-N(12)
Al(1)-N(23)
Ti‚‚‚Tia
1.977(6)
1.984(6)
2.804(2)
Al(1)-N(13)
Ti-Na
Ti‚‚‚Ala
N(12)-Al(1)-N(13)
N(13)-Al(1)-N(23)
C(1)-Al(1)-N(13)
N(12)-Al(1)-N(23)
C(1)-Al(1)-N(12)
C(1)-Al(1)-N(23)
90.3(2)
121.2(3)
125.7(3)
93.6(2)
88.0(2)
resonance signals for 8 as the major product along with
minor broad resonances that could be due to paramagnetic
species. Despite many attempts 8 could not be obtained in a
a
a
N(1)-Ti-Nimido
Nimido-Ti-Nimido
Ti-N-Tia
Ti-N-Ala
1
13
1
pure form and was only characterized by H and C{ H} NMR
spectroscopy.29
a
Averaged values
In contrast, the heating of the trimethylsilylmethyl aluminum
adduct 3 in toluene at 90 °C in the absence of light progressed
[C10H20N4](AlMe3)2],7a and [AlMe(OEP)]30 (OEP ) 2,3,7,8,-
12,13,17,18-octaethylporphinato).
cleanly to give the analogous complex [(Me3SiCH2)Al{(µ3-N)2-
5
(
(
µ3-NH)Ti3(η -C5Me5)3(µ3-N)}] (9) as a red solid in 82% yield
Scheme 2). The thermal decomposition of 3 in benzene-d6
The thermal behavior of the benzyl gallium (6) and indium
(7) adducts in benzene-d6 was also investigated by NMR
spectroscopy. Both complexes decompose, slowly at room
temperature and rapidly at higher temperatures, giving different
products. Upon heating 6 at 110 °C for 1 day the monobenzyl
solution was monitored by NMR spectroscopy. Spectra taken
after heating at 50 °C showed new resonances assigned to the
dialkylaluminum compound [(Me3SiCH2)2Al{(µ3-N)(µ3-NH)2-
5
5
Ti3(η -C5Me5)3(µ3-N)}] (10) and tetramethylsilane. After 3 days
gallium(III) derivative [(C6H5CH2)Ga{(µ3-N)2(µ3-NH)Ti3(η -
1
31
at that temperature, the H NMR spectrum revealed a mixture
C5Me5)3(µ3-N)}] (11) and toluene (1:2 ratio) were observed.
of 10 (ca. 70%) and complexes 3 and 9. After heating at 90 °C
for 20 h, the spectra revealed complete consumption of 3 and
However, the data for the decomposition studies of the indium
adduct 7 at that temperature indicated the formation of toluene,
5
1
0 to give complex 9 and the corresponding 2 equiv of
bibenzyl, and the indium(I) complex [In{(µ3-N)(µ3-NH)2Ti3(η -
tetramethylsilane. It is noteworthy that although one NH group
remains in complexes 8 and 9, no further alkane elimination
occurs on heating those compounds in benzene-d6 solutions at
C5Me5)3(µ3-N)}] (12) in a 1:1:1 ratio.
In preparative scale experiments, complex 11 could not be
isolated in a pure form due to the presence of small impurities
of 1, which shows similar solubility in common solvents. The
thermal decomposition of the benzyl indium derivative 7 in
toluene at 130 °C for 3 days afforded a mixture of 12 and
bibenzyl. Alternatively, heating of complex 7 in the solid state
under dynamic vacuum at 200 °C for 12 h afforded complex
12 in quantitative yield. We had previously published the
synthesis and characterization of 12 through the reaction of the
1
80 °C.
Compound 9 was characterized by spectroscopic and analytic
methods as well as by an X-ray crystal structure determination.
1
H NMR spectra of complexes 8 and 9 in benzene-d6 reveal
5
resonance signals for two η -C5Me5 groups in a 1:2 ratio, those
due to one alkyl ligand and broad signals for the NH imido
ligand. These data are consistent with Cs-symmetry in solution.
The molecular structure of the azaheterometallocubane 9 is
presented in Figure 3, while selected lengths and angles are
given in Table 2. Complex 9 shows an almost perfect [AlTi3N4]
cube core with angles M-N-M, N-Al-N, and N-Ti-N all
close to 90°. The coordination environment of aluminum is best
described as distorted tetrahedral with angles spanning 90.2-
5
lithium derivative [Li(µ4-N)(µ3-NH)2{Ti3(η -C5Me5)3(µ3-N)}]2
1
6
(2) with InCl in toluene.
In view of these results, the thermal decomposition of adducts
of 1 with group 13 trialkyl derivatives appears to proceed in a
first step via elimination of an alkane molecule to give dialkyl
5
intermediates [R2M{(µ3-N)(µ3-NH)2Ti3(η -C5Me5)3(µ3-N)}], un-
(
2)-127.9(4)°. The bond lengths Al-C, 1.946(8) Å, and Al-
ambiguously identified in the bis(trimethylsilylmethyl)aluminum
N, average 1.981(6) Å, are similar to those found in the
aluminum macrocyclic complexes [AlEt(C22H22N4)], [(AlMe)2-
9
(30) Guilard, R.; Zrineh, A.; Tabard, A.; Endo, A.; Han, B. C.; Lecomte,
C.; Souhassou, M.; Habbou, A.; Ferhat, M.; Kadish, K. M. Inorg. Chem.
1
990, 29, 4476-4482.
(
29) NMR data for 8: 1H NMR (C6D6, 20 °C, δ): 8.47 (s br, 1H; NH),
(31) NMR data for 11: 1H NMR (C6D6, 20 °C, δ): 8.26 (s br, 1H; NH),
13
2
{
-
.20 (s, 15H; C5Me5), 2.01 (s, 30H; C5Me5), -0.37 (s, 3H; AlMe). C-
7.20-6.90 (m, 5H; C6H5), 2.34 (s, 2H; CH2), 2.20 (s, 15H; C5Me5), 1.98
(s, 30H; C5Me5). C{ H} NMR (C6D6, 20 °C, δ): 141.5, 128.7, 128.1,
124.3 (C6H5), 118.5, 117.9 (C5Me5), 16.3 (Ga-CH2), 12.1, 12.0 (C5Me5).
1
13 1
H} NMR (C6D6, 20 °C, δ): 118.7, 118.2 (C5Me5), 12.0, 11.9 (C5Me5),
17.0 (AlMe).

4
12 Organometallics, Vol. 26, No. 2, 2007
Garc ´ı a-Castro et al.
Scheme 3. Reactions with Chloromethyl Complexes
5
[AlCl3-nMe
n
] and [MClMe
3
] ([Ti] ) Ti(η -C
5
Me
5
))
Figure 4. Perspective view of 13‚C
the 50% probability level.
7
H
8
with thermal ellipsoids at
Table 3. Selected Bond Lengths (Å) and Angles (deg) for
3‚C
1
7 8
H
Al(1)-N(23)
1.902(2)
2.185(1)
2.833(1)
2.055(2)
2.049(2)
1.958(2)
117.5(1)
111.6(1)
109.3(1)
121.1(1)
88.9(1)
Al(1)-C(1)
1.977(3)
2.163(1)
1.919(2)
1.887(3)
1.878(2)
1.958(2)
101.8(1)
110.2(1)
105.6(1)
119.8(1)
94.2(1)
Al(1)-Cl(1)
Al(1)-Cl(2)
Ti‚‚‚Tia
Ti-N(1)a
Ti(2)-N(23)
Ti(2)-N(12)
Ti(3)-N(23)
Ti(3)-N(13)
derivative 10. From those intermediates, an additional alkane
elimination affords the aluminum and gallium monoalkyl
derivatives 8, 9, and 11. This pathway is comparable to those
reported for the chemistry of aluminum, gallium, and indium
Ti(1)-N(12)
Ti(1)-N(13)
N(23)-Al(1)-C(1)
N(23)-Al(1)-Cl(2)
C(1)-Al(1)-Cl(2)
Al(1)-N(23)-Ti(2)
Ti(2)-N(23)-Ti(3)
Ti-N(1)-Tia
N(23)-Al(1)-Cl(1)
C(1)-Al(1)-Cl(1)
Cl(1)-Al(1)-Cl(2)
Al(1)-N(23)-Ti(3)
9
10
a
with macrocyclic secondary amines by Ito and other authors.
Ti-(µ -NH)-Ti
2
a
In contrast, the formation of the indium(I) complex 12, toluene,
and bibenzyl may be explained as a result of the reductive
elimination reaction from the undetected intermediate [(C6H5-
95.2(1)
105.9(1)
N(1)-Ti-Nimido
85.9(1)
Nimido-Ti-Nimidoa
a
Averaged values
5
CH2)2In{(µ3-N)(µ3-NH)2Ti3(η -C5Me5)3(µ3-N)}]. An analogous
decomposition of indium(III) to indium(I) derivatives in orga-
117.5(1)°. The Al-N distance of 1.902(2) Å is shorter than
those found in 9 (average 1.981(6) Å) but similar to that found
1
nometallic chemistry has been observed upon heating [In(η -
5
32
33
C5H5)3], in the solid state or solution, to give [In(η -C5H5)].
in [MeCl Al{N(SnMe ) }], 1.919(8) Å. The Al-N, Al-C
2
3 3
Reactions with Group 13 and 14 Chloromethyl Deriva-
tives. Treatment of [{Ti(η -C5Me5)(µ-NH)}3(µ3-N)] (1) with 1
(1.977(3) Å), and Al-Cl (average 2.174(1) Å) bond lengths in
13 compare well with those recently reported for [MeCl2Al-
5
t
34
equiv of dichloromethylaluminum [AlCl2Me] or chlorodi-
methylaluminum [AlClMe2] derivatives at room temperature led
(NH2 Bu)]. The sum of angles M-N(23)-M (329.8°) is very
close to an ideal tetrahedral geometry. Within the organometallic
ligand the coordination of one NH group to aluminum gives a
0.1 Å lengthening of the Ti-N(23) bonds and a Ti(2)-N(23)-
5
to the adducts [MenCl3-nAl{(µ3-NH)3Ti3(η -C5Me5)3(µ3-N)}] (n
)
[
1 (13), 2 (14)) (Scheme 3). Whereas the reaction of 1 with
AlCl2Me] in toluene afforded compound 13‚C7H8 in high purity
11
Ti(3) angle 4° narrower than that of 1, in a similar disposition
to that of 6 and 7.
as an orange precipitate in 41% yield, the analogous treatment
of 1 with [AlClMe2] gave a dark green precipitate. This green
solid is not soluble in benzene-d6 and produced orange solutions
in chloroform-d1, where complex 14 was identified by NMR
spectroscopy. Complex 14 was obtained as an orange solid (83%
yield) in higher purity by using chloroform-d1 as reaction solvent
and amber-colored glassware in all the manipulations.
Thermal decomposition of complexes 13 and 14 in benzene-
d6 solutions was examined by NMR spectroscopy. After heating
at 50 °C for 1 day, the spectra showed a complicated mixture
of unknown products. The thermal processes presumably involve
activation of aluminum-chlorine bonds with generation of
reactive HCl and were not further investigated.
Complexes 13 and 14 were characterized by spectral and
analytical techniques, as well as by an X-ray crystal structure
We have also examined the reaction of 1 with alkyl
derivatives of group 14 elements. Compound 1 did not react
1
13
1
determination for 13‚C7H8. H and C{ H} NMR spectra in
chloroform-d1 at room temperature show resonances for equiva-
with silicon or tin [MMe ] derivatives even after prolonged
4
heating at 200 °C in benzene-d solutions. The reaction of 1
6
5
lent η -C5Me5, Al-CH3, and NH groups, suggesting rapid
with chlorotrimethyltin in benzene-d was monitored by NMR
6
exchange processes in solution. Upon cooling at -50 °C, the
spectroscopy. After heating at 50 °C for 1 day the spectra
1
5
H NMR spectrum of 13 still revealed a single sharp resonance
showed resonances for the compound [Me Sn{(µ -N)Ti (η -C -
3
3
3
5
5
for the η -C5Me5 ligands. The molecular structure of complex
Me ) (µ-NH) (µ -N)}] (15) presumably via generation of HCl.
5
3
2
3
1
3 is presented in Figure 4, while selected bond lengths and
The formation of 15 at 50 °C is very slow, and at higher
angles are given in Table 3. Crystals of 13 bear one toluene
molecule per aluminum adduct. The solid-state structure presents
a distorted tetrahedral geometry for the aluminum center,
comprising two chlorine atoms, one carbon atom of a methyl
group, and one NH ligand, with angles spanning 101.8(1)-
temperatures the spectra show resonances for complexes 15, 1,
[SnMe ], and several unidentified species. Complex 15 and the
4
5
analogous silicon derivative [Me Si{(µ -N)Ti (η -C Me ) (µ-
3
3
3
5
5 3
NH) (µ -N)}] (17) have been previously obtained as orange
2
3
(
33) Cheng, Q. M.; Stark, O.; Merz, K.; Winter, M.; Fischer, R. A. J.
(
32) (a) Fischer, E. O.; Hofmann, H. P. Angew. Chem. 1957, 69, 639-
40. (b) Beachley, O. T., Jr.; MacRae, D. J.; Kovalevsky, A. Y.; Zhang,
Y.; Li, X. Organometallics 2002, 21, 4632-4640.
Chem. Soc., Dalton Trans. 2002, 2933-2936.
(34) Carmalt, C. J.; King, S. J.; Mileham, J. D.; Sabir, E.; Tocher, D. A.
Organometallics 2004, 23, 2939-2943.
6

5
Imido-Nitrido Metalloligand [{Ti(η -C
5
Me
5
)(µ-NH)}
3
(µ
3
-N)]
Organometallics, Vol. 26, No. 2, 2007 413
nitrido group in an almost perfect tetrahedral geometry. The
tin-nitrogen, 2.060(4) Å, and tin-carbon, average 2.150(5) Å,
bond lengths in 15 are similar to those found in other trimethyltin
35
amido complexes. The germanium-nitrogen, 1.861(4) Å, and
germanium-carbon, average 1.954(5) Å, bond lengths in 16
compare well with reported values in the literature for trimeth-
3
6
ylgermanium amides. As can be seen in Table 4, the tin-
nitrogen and tin-carbon bond lengths in 15 are 0.199 and 0.196
Å longer than the respective germanium bond lengths in 16,
which correspond to the difference in covalent radii of germa-
2
8
nium and tin (0.18 Å).
The sum of angles M-N-M about N(13) in 15, 343.1°, and
6, 346.2°, are slightly smaller than that expected for a trigonal
1
Figure 5. Perspective view of 15 with thermal ellipsoids at the
0% probability level.
planar geometry (360°) but bigger than the analogous sum for
the bridging nitrogen atom in the structures determined for
adducts 6, 7, and 13. Within the metalloligand the titanium-
nitrogen bond lengths (average 1.928(4) Å in 15 and 1.930(4)
Å in 16) and the Ti-N-Ti (average ≈ 93°) and N-Ti-N
5
(
average 106°) angles are very similar to those found in 1.11
1
H NMR spectra of complexes 15-17 in benzene-d6 at room
5
temperature show resonance signals for two η -C5Me5 groups
in a 2:1 ratio, singlets for the MMe3 fragments, and broad signals
for equivalent NH ligands. These data are consistent with Cs-
symmetric structures in solution. The NH resonance signals in
these spectra (δ ) 14.2-14.1) are shifted to lower field than
those found in 1 (δ ) 13.8). We have not observed this shift to
lower field in any other derivatives of 1, and we suggest that
these data are indicative of the absence of coordination of the
NH ligands to the silicon, germanium, or tin centers in solution.
The NMR data of 15-17 are therefore in agreement with the
solid-state structures and rule out the existence of six-coordinate
metal centers in solution. Thus, we propose that complexes 15-
17 both in solution and in the solid state show an incomplete
cube structure similar to the organometallic ligand 1.
Figure 6. Perspective view of 16 with thermal ellipsoids at the
50% probability level.
Table 4. Selected Lengths (Å) and Angles (deg) for
Complexes 15 and 16
M ) Sn (15)
M ) Ge (16)b
M-N(13)
2.060(4)
2.150(5)
1.928(4)
2.806(1)
109.5(2)
109.5(2)
125.9(2)
124.2(2)
93.0(2)
1.861(4)
1.954(5)
1.930(4)
2.808(1)
110.1(2)
108.9(2)
127.5(2)
126.1(2)
92.6(2)
a
M-C
a
Ti-N
a
Conclusion
Ti‚‚‚Ti
a
N(13)-M-C
a
5
C-M-C
The reaction of the organometallic ligand [{Ti(η -C5Me5)-
M-N(13)-Ti(1)
M-N(13)-Ti(3)
Ti(1)-N(13)-Ti(3)
(
µ-NH)}3(µ3-N)] (1) with alkyl group 13 derivatives affords
5
adducts [R3M{(µ3-NH)3Ti3(η -C5Me5)3(µ3-N)}] and [MenCl3-n-
5
a
Al{(µ3-NH)3Ti3(η -C5Me5)3(µ3-N)}] in the first step. Adducts
Ti-N-Ti
N(1)-Ti-Nimido
Nimido-Ti-Nimido
93.5(2)
86.2(2)
105.9(2)
93.4(2)
86.2(2)
106.0(2)
a
of trialkyl derivatives of aluminum and gallium further react at
a
moderate temperatures to form monoalkyl derivatives [RM{(µ3-
a
Averaged values b Averaged values for the two independent molecules
5
N)2(µ3-NH)Ti3(η -C5Me5)3(µ3-N)}] via elimination of 2 equiv
in the asymmetric unit.
of alkane. In contrast, the indium tribenzyl adduct of 1 releases
toluene in the first step and later a reductive elimination reaction
takes place, affording the indium(I) complex [In{(µ3-N)(µ3-
5
crystals by treatment of [Li(µ4-N)(µ3-NH)2{Ti3(η -C5Me5)3(µ3-
N)}]2 (2) with [MClMe3] in toluene at room temperature
5
NH)2Ti3(η -C5Me5)3(µ3-N)}] and bibenzyl. On the other hand,
1
6
(
Scheme 3). The reaction of 2 with chlorotrimethylgermanium
highly stable trimethyl derivatives of group 14 elements [Me3M-
5
afforded the new complex [Me3Ge{(µ3-N)Ti3(η -C5Me5)3(µ-
NH)2(µ3-N)}] (16) in 88% yield. Compounds 15-17 are very
soluble in hexane or toluene, and their solutions in benzene-d6
remain unaltered at high temperatures. Complex 16 features
similar spectroscopic data to those reported for 15 and 17. In
addition, from saturated pentane solutions of 15 and 16 at -40
C it was possible to grow suitable single crystals for X-ray
5
{
(µ3-N)Ti3(η -C5Me5)3(µ-NH)2(µ3-N)}] with incomplete cube
structure can be obtained through the reaction of the lithium
5
reagent [Li(µ4-N)(µ3-NH)2{Ti3(η -C5Me5)3(µ3-N)}]2 (2) with
[MClMe3].
1
6
(35) For some examples, see: (a) Dilworth, J. R.; Hanich, J.; Krestel,
°
M.; Beck, J.; Str a¨ hle, J. J. Organomet. Chem. 1986, 315, C9-C12. (b)
Stalke, D.; Klingebiel, U.; Sheldrick, G. M. J. Organomet. Chem. 1988,
diffraction. The molecular structures of 15 and 16 are shown
in Figures 5 and 6, while selected bond lengths and angles for
both complexes are given in Table 4. Complex 16 crystallizes
with two independent molecules in the asymmetric unit. The
solid-state structures of 15 and 16 reveal the coordination of
the metalloligand by one µ3-N nitrido group to the tin and
germanium centers, respectively. The coordination sphere of
the group 14 elements contains three methyl groups and the
3
41, 119-124. (c) Bai, Y.; Roesky, H. W.; Schmidt, H.-G.; Noltemeyer,
M. Z. Naturforsch. 1992, B47, 603-608. (d) Hillwig, R.; Harms, K.;
Dehnicke, K. J. Organomet. Chem. 1995, 501, 327-332.
(36) For some examples, see: (a) Halder, T.; Schwarz, W.; Weidlein,
J.; Fischer, P. J. Organomet. Chem. 1983, 246, 29-48. (b) Hausen, H. D.;
Mundt, O.; Kaim, W. J. Organomet. Chem. 1985, 296, 321-337. (c) Miller,
G. A.; Lee, S. W.; Trogler, W. C. Organometallics 1989, 8, 738-744. (d)
Trapp, M.; Hausen, H. D.; Weckler, G.; Weidlein, J. J. Organomet. Chem.
1993, 450, 53-61.

4
14 Organometallics, Vol. 26, No. 2, 2007
Table 5. Experimental Data for the X-ray Diffraction Studies on 6, 7, 9, 13‚C
Garc ´ı a-Castro et al.
8
H , 15, and 16
7
formula
C51H69GaN4Ti3
C51H69InN4Ti3
(7)
996.62
C34H57AlN4SiTi3
(9)
720.61
C38H59AlCl2N4Ti3
(13‚C7H8)
813.47
C33H56N4SnTi3
(15)
771.21
C33H56GeN4Ti3
(16)
725.11
(6)
Mr
951.52
T [K]
200(2)
100(2)
200(2)
150(2)
100(2)
100(2)
λ [Å]
0.71073
monoclinic
P21/n
0.71073
monoclinic
P21/n
0.71073
monoclinic
P2(1)/n
0.71069
monoclinic
P21/c
0.71073
triclinic
P1h
0.71073
triclinic
P1h
cryst syst
space group
a [Å]; R [deg]
11.848(2)
11.841(2)
11.135(1)
18.467(5)
11.512(1);
11.029(2);
111.66(1)
17.912(2);
90.19(1)
19.780(1);
102.22(1)
3535.1(8)
4
95.60(1)
b [Å]; â [deg]
c [Å]; γ [deg]
17.045(3);
17.002(2);
91.44(1)
24.252(3)
23.600(3);
101.56(1)
15.116(1)
11.320(5);
103.73(1)
20.250(5)
12.096(1);
100.52(1)
13.315(2);
91.38(1)
24.126(5)
98.43(1)
V [Å3]
Z
4871.0(15)
4
1.298
1.058
2000
4881(1)
4
1.356
0.977
2072
3891.5(7)
4
1.230
0.681
1528
4112(2)
4
1.314
0.751
1712
1788.3(3)
2
1.432
1.362
796
-
3
Fcalcd [g cm
]
1.362
1.522
1520
µMoKR [mm-1]
F(000)
cryst size [mm]
0.15 × 0.15 ×
0.52 × 0.33 ×
0.20 × 0.15 ×
0.67 × 0.42 ×
0.69 × 0.43 ×
0.55 × 0.32 ×
0
.15
0.33
0.13
0.19
0.09
0.21
θ range [deg]
3.05 to 27.50
-15 to 15,
5.02 to 27.50
-15 to 15,
-22 to 22,
-31 to 31
38 873
5.06 to 20.00
-10 to 10,
-22 to 22,
-14 to 14
13 850
3.15 to 27.52
-23 to 23,
-14 to 14,
-26 to 26
82 307
5.10 to 27.50
-14 to 14,
-15 to 15,
-17 to 17
67 791
5.01 to 27.00
-14 to 14,
-22 to 22,
-25 to 25
104 445
index ranges
-
-
22 to 21,
31 to 31
39 326
no. of reflns
collected
no. of unique data
11 173
11 138
3572
9442
8166
15 301
[
Rint ) 0.101]
[Rint ) 0.074]
8070
[Rint ) 0.089]
2472
[Rint ) 0.151]
7084
[Rint ) 0.188]
6444
[Rint ) 0.145]
11 405
no. of obsd data
7970
[
I > 2σ(I)]
goodness-of-fit
on F
0.912
0.944
1.041
1.056
1.093
1.125
2
final R indices
R1 ) 0.044,
wR2 ) 0.097
R1 ) 0.075,
wR2 ) 0.111
0.533/-0.495
R1 ) 0.040,
wR2 ) 0.079
R1 ) 0.071,
wR2 ) 0.090
0.802/-0.582
R1 ) 0.054,
wR2 ) 0.126
R1 ) 0.092,
wR2 ) 0.149
0.341/-0.386
R1 ) 0.048,
wR2 ) 0.108
R1 ) 0.076,
wR2 ) 0.124
0.499/-0.615
R1 ) 0.052,
wR2 ) 0.126
R1 ) 0.072,
wR2 ) 0.139
1.544/-1.988
R1 ) 0.056,
wR2 ) 0.140
R1 ) 0.087,
wR2 ) 0.168
1.732/-0.985
[
I > 2σ(I)]
R indices
(all data)
largest diff peak/
-
3
hole [e Å
]
a
R1 ) ∑||Fo| - |Fc||/[∑|Fo|] wR2 ) {[∑w(Fo - Fc ) ]/[∑w(Fo ) ]}1/2.
2
2 2
2 2
Experimental Section
using amber-colored glassware. A 100 mL amber-colored Schlenk
flask was charged with 1 (0.50 g, 0.82 mmol), [Al(CH SiMe
0.24 g, 0.83 mmol), and hexane (20 mL). The reaction mixture
was stirred at room temperature for 2 h with precipitation of a solid.
This solid was isolated by filtration onto a glass frit, washed with
hexane (15 mL), and vacuum-dried to afford 3 as a yellow powder
2
3 3
) ]
General Comments. All manipulations were carried out under
(
argon atmosphere using Schlenk line or glovebox techniques.
Hexane was distilled from Na/K alloy just before use. Toluene was
freshly distilled from sodium. NMR solvents were dried with Na/K
alloy (C
6 6 3
D ) or calcium hydride (CDCl ) and vacuum-distilled.
-
1
(
0.47 g, 63%). IR (KBr, cm ): 3361 (w), 2946 (vs), 2910 (vs),
1493 (w), 1431 (m), 1377 (s), 1322 (w), 1238 (vs), 1025 (w), 961
s), 858 (vs), 824 (vs), 788 (w), 754 (vs), 735 (vs), 675 (w), 657
Oven-dried glassware was repeatedly evacuated with a pumping
-
3
system (ca. 1 × 10 Torr) and subsequently filled with inert gas.
Thermolyses in solution at high temperatures were carried out by
heating flame-sealed NMR or Carius tubes in a Roth autoclave
(
(s), 589 (m), 542 (w), 510 (w), 462 (w), 419 (w). NMR spectra
model III. [AlMe
AlClMe ] (1 M in hexane), and bibenzyl were purchased from
Aldrich and used as received. [GeClMe ] was purchased from
3
] (2 M in toluene), [AlCl
2
Me] (1 M in hexane),
were obtained from solutions of 3 in amber-colored NMR tubes.
1
[
2
6 6
H NMR (C D , 20 °C, δ): 12.44 (s br, 3H; NH), 1.94 (s, 45H;
13
1
3
C Me ), 0.38 (s, 27H; SiMe ), -1.04 (s, 6H; CH ). C{ H} NMR
5
5
3
2
5
ABCR and used as received. [{Ti(η -C
5
Me
-N)}]
] (M ) Al, Ga, In ), [Ga(CH
5
)(µ-NH)}
3
(µ
7 8
3
-N)]
6 6 5 5 5 5 3
(C D , 20 °C, δ): 120.3 (C Me ), 12.4 (C Me ), 4.4 (SiMe ), not
11,12
5
16
(
[
[
1),
M(CH
In(CH
[Li(µ
4
-N)(µ
3
-NH)
2
{Ti
3
(η -C
5
Me
5
)
3
(µ
3
2
‚C (2‚C H ),
7
H
8
observed AlCH
2
. MS (EI, 70 eV): m/z (%) 722 (18) [M -
3
7
19
38
21
2
SiMe
3
)
3
2
6 5 3
C H ) (thf)], and
+
+
2
(SiMe
4
)] , 608 (15) [M - Al(CH
] , 115 (7) [Al(CH
2
SiMe
)] , 73 (100) [SiMe
3
)
3
] , 202 (13) [Al(CH
2
-
2
C H
2 6 5
)
3
]2 were prepared according to published procedures.
+
+
+
SiMe
)
3 2
2
SiMe
(M
.25. Found: C 56.06, H 9.29, N 5.96.
Synthesis of [(Me SiCH Ga{(µ -NH)
4). In a fashion similar to the preparation of 3, treatment of 1 (0.50
g, 0.82 mmol) with [Ga(CH SiMe ] (0.30 g, 0.90 mmol) in hexane
3
3
] . Anal.
Samples for infrared spectroscopy were prepared as KBr pellets.
H and C NMR spectra were recorded on a Varian Unity-300
Calcd for C42
H81AlN
4
Si
3
Ti
3
w
) 896.97): C 56.24, H 9.10, N
1
13
6
spectrometer. Chemical shifts (δ) are given relative to residual
protons or to carbon of the solvent. Electron impact mass spectra
were obtained at 70 eV on a Hewlett-Packard 5988A mass
spectrometer. Microanalyses (C, H, N) were performed in a Heraeus
5
3
)
2 3
3
3 3 5 5 3 3
Ti (η -C Me ) (µ -N)}]
(
2
3 3
)
CHN-O-Rapid or a Leco CHNS-932 microanalyzer.
(20 mL) for 9 h afforded 4 as an orange solid (0.33 g, 43%). IR
(KBr, cm ): 3343 (w), 2942 (vs), 2913 (vs), 2858 (m), 1590 (w),
5
-1
3 2 3 3 3 3 5
Synthesis of [(Me SiCH ) Al{(µ -NH) Ti (η -C Me
5 3 3
) (µ -N)}]
(3). All manipulations were carried out in the absence of light by
1489 (m), 1434 (m), 1377 (m), 1233 (s), 1161 (w), 1024 (w), 911
(
5
s), 855 (s), 822 (vs), 756 (m), 720 (vs), 676 (w), 648 (s), 621 (w),
(
37) Tessier-Youngs, C.; Beachley, O. T., Jr. Inorg. Synth. 1986, 24,
29 (w), 496 (w), 474 (w), 428 (w). MS (EI, 70 eV): m/z (%) 678
9
2-93.
+
+
(1) [M - 3(CH
2
SiMe
3
+
)] , 608 (1) [M - Ga(CH
2
SiMe
3
)
3
] , 243
(38) Kopasz, J. P.; Hallock, R. B.; Beachley, O. T., Jr. Inorg. Synth.
+
+
1
986, 24, 89-91.
(35) [Ga(CH SiMe
2
3
)
2
] , 157 (2) [Ga(CH
2
SiMe
3
)] , 73 (49) [SiMe
3
] .

5
Imido-Nitrido Metalloligand [{Ti(η -C
5
Me
5
)(µ-NH)}
3
(µ
3
-N)]
Organometallics, Vol. 26, No. 2, 2007 415
1
Anal. Calcd for C42 Si Ti (M
H
81GaN
4
3
3
w
) 939.71): C 53.68, H
-0.69 (s, 2H; AlCH
118.3 (C Me
AlCH . MS (EI, 70 eV): m/z (%) 722 (42) [M] , 609 (18) [M -
2
). 13C{ H} NMR (C
6
D
6
, 20 °C, δ): 118.7,
3
+
8.69, N 5.96. Found: C 54.06, H 8.58, N 6.40.
5
5
), 12.0, 11.9 (C
5
Me
5
), 2.5 (SiMe ), not observed
5
Synthesis of [(Me
5). In a fashion similar to the preparation of 3, treatment of 1 (0.50
g, 0.82 mmol) with [In(CH SiMe ] (0.31 g, 0.82 mmol) in hexane
25 mL) for 5 h afforded 5 as an orange solid (0.36 g, 44%). IR
3 2 3 3
SiCH ) In{(µ -NH)
3
Ti
3
(η -C
5 5 3 3
Me ) (µ -N)}]
2
+
+
Al(CH
2
SiMe
3 3 4
)] , 73 (100) [SiMe ] . Anal. Calcd for C34H57AlN -
) 720.52). C 56.68, H 7.97, N 7.78. Found: C 56.50,
(
SiTi (M
3
w
2
3 3
)
H 8.24, N 7.13.
(
(
1
-
1
KBr, cm ): 3344 (m), 2941 (vs), 2915 (vs), 1492 (w), 1436 (m),
378 (m), 1233 (s), 1164 (w), 1102 (w), 1068 (w), 1023 (w), 879
Thermal Decomposition of 3 in a NMR Tube Scale Experi-
ment. A 5 mm amber-colored valved-NMR tube was charged with
5
(
(
(
[
s), 853 (vs), 821 (s), 720 (vs), 646 (vs), 548 (w), 473 (w), 427
[(Me
SiCH )
3 2 3
Al{(µ
3
-NH)
3
Ti
3
(η -C
5
Me
5
)
3
(µ
3
-N)}] (3) (0.020 g,
+
m). MS (EI, 70 eV): m/z (%) 723 (1) [M - 3(CH
2
SiMe
3
)
3
] , 608
0.016 mmol) and benzene-d
6
(1.00 mL). The reaction course was
+
+
2) [M - In(CH
2
SiMe
3
+
)
3
] , 289 (46) [In(CH
2
SiMe
3
)
2
] , 115 (100)
monitored by NMR spectroscopy at different temperatures. After
heating at 50 °C in an oil bath for 4 h, the spectra revealed new
resonances assigned to the dialkylaluminum compound [(Me -
3
2 2 3 3 2 3 5 5 3 3
SiCH ) Al{(µ -N)(µ -NH) Ti (η -C Me ) (µ -N)}] (10) and tet-
ramethylsilane. Upon leaving the tube at this temperature for 3 days,
the H NMR spectrum showed 10 as the major product (ca. 70%)
of a mixture of this complex with 3 and 9. After heating at 90 °C
for 20 h, the spectra revealed complete consumption of 3 and 10
to give complex 9 and the corresponding 2 equiv of SiMe
+
In] , 73 (51) [SiMe
3
] . Anal. Calcd for C42
H81InN
4
Si
3
Ti
3
(M
w
)
9
5
84.81): C 51.22, H 8.29, N 5.69. Found: C 51.18, H 7.98, N
.80.
5
5
6 5 2 3 3
Synthesis of [(C H CH ) Ga{(µ -NH)
3
Ti
3
(η -C
5 5 3 3
Me ) (µ -N)}]
1
(6). A solution of [Ga(CH
2
C
H
6 5
3
) (thf)] (0.34 g, 0.49 mmol) in
toluene (10 mL) was carefully added to 1 (0.30 g, 0.49 mmol) in
toluene (20 mL). The system was allowed to react without any
stirring for 2 days. After decantation, 6 was obtained as orange
4
.
5
-
1
NMR data for [(Me SiCH ) Al{(µ -N)(µ -NH) Ti (η -C Me ) -
crystals (0.24 g, 51%). IR (KBr, cm ): 3349 (m), 3047 (w), 3014
w), 2909 (vs), 2860 (w), 1595 (s), 1488 (s), 1448 (m), 1430 (m),
376 (s), 1309 (w), 1204 (s), 1178 (w), 1067 (vs), 1026 (m), 996
m), 894 (w), 839 (m), 798 (s), 751 (vs), 731 (vs), 697 (vs), 651
3
2 2
3
3
2
3
5
5 3
(µ
3
-N)}] (10): 1H NMR (C
6
D
6
, 20 °C, δ): 10.23 (s br, 2H; NH),
Me ), 0.33 (s, 18H; SiMe ),
). C{ H} NMR (C , 20 °C, δ): 120.1,
(
1
2
-
.05 (s, 30H; C
0.90 (s, 4H; AlCH
5
Me
5
), 1.90 (s, 15H; C
5
5
3
13
1
2
6 6
D
(
(
1
119.2 (C Me ), 12.3, 11.9 (C Me ), 4.1 (SiMe ), not observed
vs), 591 (s), 539 (w), 517 (w), 462 (m), 447 (m), 420 (w). H
, 20 °C, δ): 12.50 (s br, 3H; NH), 7.13 (m, 6H;
), 6.93 (m, 3H; p-C ), 6.64 (m, 6H; o-C ), 1.86 (s,
Me ), 1.74 (s, 6H; CH , 20 °C, δ):
48.1 (m, ipso-C ), 127.5 (m, JC-H ) 156 Hz; o-C ), 127.1
), 120.5 (m, JC-H ) 159 Hz; p-C ),
5
5
5
5
3
AlCH
Thermal Decomposition of [C
3
Me (µ -N)}] (7). In Solution. A 100 mL Carius tube was
charged with 7 (0.20 g, 0.20 mmol) and toluene (30 mL). The tube
was flame-sealed and heated at 130 °C for 3 days. The tube was
opened in the glovebox and the solution filtered. The volatile
components of the solution were removed under reduced pressure
2
.
NMR (C
m-C
4
1
6 6
D
H
5H; C
5
6
H
5
H
6 5
6
5
CH
2
)
3
3 3 3
In{(µ -NH) Ti
(η5-
H
6
13
). C NMR (CDCl
3
C
5
5
)
3
5
5
2
1
H
6 5
H
6 5
1
1
(m, JC-H ) 155 Hz; m-C
6
1
H
5
6 5
H
1
1
1
20.3 (s, C
5
Me
Me
5
2
), 27.3 (t, JC-H ) 129 Hz; CH ), 12.2 (q, JC-H )
26 Hz; C
5
5
). MS (EI, 70 eV): m/z (%) 768 (1) [M - 2(CH
2
+
-
+
+
to give a sticky, orange solid. Analysis of the solid by
H} NMR spectroscopy showed resonances for complex [In{(µ -
1H and 13C-
Ph)] , 676 (7) [M - 3(CH
5
C
(
2
Ph)] , 609 (29) [M - Ga(CH
5
2
Ph)
3
] ,
+
{
1
41 (8) [M - 3(CH
2
Ph) - C
Me
5
] , 474 (6) [M - Ga(CH
2
Ph)
3
-
3
+
+
N)(µ -NH) Ti (η
5
-C Me ) (µ -N)}] (12),16 along with those due to
5
Me
5
] , 405 (10) [M - 3(CH
2
Ph) - 2C
5
Me
5
] , 251 (41) [Ga-
2
Ph] , 69 (100)
3
2
3
5 5 3 3
+
+
+
bibenzyl, assigned by comparison with spectra obtained from a
commercially available bibenzyl sample.
In the Solid State. Complex 7 (0.15 g, 0.15 mmol) was heated
in a horizontal tube furnace at 200 °C under dynamic vacuum (ca.
.1 mmHg) for 12 h. Examination of the orange residue (0.11 g,
00%) by NMR spectroscopy revealed complete consumption of
and resonances for pure 12.
CH
2
+
Ph)
2
] , 160 (15) [Ga(CH
2
Ph)] , 91 (86) [CH
[
Ga] . Anal. Calcd for C51
H69GaN
4
3
Ti (M ) 951.46): C 64.38,
w
H 7.31, N 5.89. Found: C 64.48, H 7.42, N 5.72.
5
Synthesis of [(C
6
H
5
CH
2
)
3
In{(µ
3
-NH)
3
Ti
3
(η -C
5
Me
5
)
3
(µ
3
-N)}]
0
1
7
(
7). In a fashion similar to the preparation of 6, treatment of 1 (0.30
g, 0.49 mmol) with [In(CH ] (0.19 g, 0.49 mmol) in toluene
30 mL) for 2 days afforded 7 as orange crystals (0.29 g, 59%). IR
2 6 5 3
C H )
(
(
1
-
1
5
KBr, cm ): 3349 (m), 3048 (w), 3014 (w), 2908 (vs), 2857 (w),
595 (s), 1486 (s), 1448 (m), 1430 (m), 1376 (s), 1304 (w), 1261
NMR data for [In{(µ
3
-N)(µ
3
-NH)
2
Ti
3
(η -C
5
Me
5
)
(µ
3 3
-N)}] (12):
1
H NMR (C
Me ), 1.86 (s, 15H; C
117.9, 117.2 (C Me ), 12.0, 11.9 (C
NMR data for bibenzyl: 1H NMR (C
6 6
D , 20 °C, δ): 11.61 (s br, 2H; NH), 2.09 (s, 30H;
13
1
(
(
(
(
(
w), 1205 (vs), 1178 (w), 1029 (s), 1016 (s), 990 (s), 890 (w), 839
C
5
5
5
Me
5
). C{ H} NMR (C
Me ).
6 6
D , 20 °C, δ):
m), 796 (s), 749 (vs), 731 (vs), 696 (vs), 652 (vs), 628 (w), 596
5
5
5
5
1
s), 538 (w), 465 (m), 422 (m). H NMR (C
D
6 6
, 20 °C, δ): 12.69
), 6.91 (m, 3H; p-C ), 6.76
Me ), 1.89 (s, 6H; CH
, 20 °C, δ): 148.8 (m, ipso-C
6
D
6
, 20 °C, δ): 7.15-6.97
13
1
s br, 3H; NH), 7.18 (m, 6H; m-C
m, 6H; o-C ), 1.91 (s, 45H; C
6
H
5
5
6
H
5
(m, 10H; C
δ): 142.0 (ipso-C
), 38.2 (CH ).
6
H
5
), 2.73 (s, 4H; CH
2
). C{ H} NMR (C
6
D
6
, 20 °C,
13
H
6 5
5
2
).
C
H
6 5
), 128.8 (o-C
6
H
5
), 128.6 (m-C H ), 126.2 (p-
6 5
1
NMR (CDCl
155 Hz; o-C
3
H
6 5
), 127.8 (m, JC-H
C
6
H
5
2
1
5
)
6
H
5
), 126.2 (m, JC-H ) 152 Hz; m-C ), 120.0
6
H
5
1
Synthesis of [MeCl Al{(µ -NH) Ti (η -C Me ) (µ -N)}] (13).
2
3
3
3
5
5 3
3
1
(
m, JC-H ) 164 Hz; p-C
6
H
5
), 120.0 (s, C
5
Me
Me
5
), 26.9 (t, JC-H
)
A solution of [AlCl Me] (1 M in hexane) (1.00 mL, 1.00 mmol) in
toluene (10 mL) was added dropwise to 1 (0.60 g, 0.99 mmol) in
2
1
1
27 Hz; CH
2
), 12.1 (q, JC-H ) 125 Hz; C
5
5
). MS (EI, 70 eV):
+
+
m/z (%) 722 (6) [M - 3(CH
5
2
Anal. Calcd for C51H69InN Ti (M ) 996.55): C 61.47, H 6.98,
4 3 w
N 5.62. Found: C 61.07, H 7.01, N 4.96.
2
Ph)] , 608 (2) [M - In(CH
5
2
Ph)
3
] ,
toluene (20 mL) in an amber-colored Schlenk flask. The reaction
mixture was stirred at room temperature for 1 h to give the
precipitation of an orange solid. This solid was isolated by filtration
onto a glass frit and vacuum-dried to afford 13‚C H as an orange
powder (0.33 g, 41%). IR (KBr, cm ): 3359 (m), 3345 (w), 3271
(w), 2912 (vs), 2857 (m), 1605 (w), 1494 (w), 1428 (m), 1377 (s),
1261 (w), 1176 (m), 1067 (w), 1024 (m), 894 (s), 738 (vs), 713
+
88 (5) [M - 3(CH
2
Ph) - C
Me
5
] , 451 (9) [M - 3(CH
2
Ph) -
+
+
+
C Me
5 5
] , 315 (22) [M - 3(CH
2
5 5
Ph) - 3C Me ] , 115 (100) [In] .
7
8
-
1
5
Synthesis of [(Me SiCH )Al{(µ -N) (µ -NH)Ti (η -C Me ) (µ -
3
2
3
2
3
3 5 5 3 3
N)}] (9). A 100 mL amber-colored ampule (Teflon stopcock) was
charged with 3 (0.50 g, 0.56 mmol) and toluene (40 mL). After
stirring at 90 °C for 4 days, the volatile components were removed
under reduced pressure to afford 9 as a red solid (0.33 g, 82%). IR
1
(s), 659 (vs), 619 (vs), 557 (w), 487 (w), 466 (s), 424 (s). H NMR
(CDCl
3
, 20 °C, δ): 11.75 (s br, 3H; NH), 2.07 (s, 45H; C
5
Me
, 20 °C, δ): 121.6
), -4.34 (br AlMe). Anal. Calcd for C38
) 813.40): C 56.11, H 7.31, N 6.89. Found: C
5
),
13
1
-1.14 (s, 3H; AlMe). C{ H} NMR (CDCl
3
-
1
(
2
(
(
2
KBr, cm ): 3377 (w), 3352 (w), 2948 (s), 2910 (vs), 2854 (s),
721 (w), 1435 (m), 1375 (s), 1243 (s), 1024 (w), 971 (s), 827
vs), 726 (vs), 699 (vs), 674 (vs), 652 (vs), 625 (m), 592 (w), 456
(C
AlCl
5
Me
5
), 12.2 (C
Ti (M
5
Me
5
59
H -
2
N
4
3
w
56.00, H 7.22, N 6.72.
Synthesis of [Me ClAl{(µ
A solution of [AlClMe ] (1 M in hexane) (0.50 mL, 0.50 mmol) in
1
5
m), 441 (m). H NMR (C
.20 (s, 15H; C Me ), 2.02 (s, 30H; C
D
6 6
, 20 °C, δ): 9.18 (s br, 1H; NH),
Me ), 0.16 (s, 9H; SiMe ),
2
3 3 3 5 5 3 3
-NH) Ti (η -C Me ) (µ -N)}] (14).
5
5
5
5
3
2

4
16 Organometallics, Vol. 26, No. 2, 2007
Garc ´ı a-Castro et al.
chloroform-d
g, 0.49 mmol) in chloroform-d
Schlenk flask. The reaction mixture was stirred at room temperature
for 15 min to give an orange solution. The volatile components
were removed under reduced pressure to give 14 as an orange solid
1
(10 mL) was added dropwise to a solution of 1 (0.30
(20 mL) in an amber-colored
molybdenum radiation was used in all cases, graphite monochro-
mated, and enhanced with a MIRACOL collimator. Crystallographic
data for all the complexes are presented in Table 5.
1
Multiscan39 (6, 7, and 9) or analytical (13, 15, and 16)
40
absorption correction procedures were applied to the data. The
-
1
41
(0.29 g, 83%). IR (KBr, cm ): 3361 (m), 3267 (m), 2913 (vs),
structures were solved, using the WINGX package, by direct
methods (SHELXS-9742 for 6, 7, 9, and 16, SIR97 for 13) or
43
1488 (w), 1428 (m), 1378 (s), 1261 (w), 1174 (m), 1067 (m), 1023
1
42
(
m), 867 (m), 735 (vs), 663 (vs), 618 (vs), 524 (w), 460 (m). H
NMR (CDCl , 20 °C, δ): 11.66 (s br, 3H; NH), 1.98 (s, 45H; C
Me
22.8 (C
Patterson techniques (SHELXS-97 for 15) and refined by least-
2
42
3
5
-
squares against F (SHELXL-97).
), -1.33 (s, 6H; AlMe). 13C{ H} NMR (CDCl
1
, 20 °C, δ):
5
3
All non-hydrogen atoms of 6 were anisotropically refined. All
the hydrogen atoms of the imido and benzyl groups were located
in the difference Fourier map and refined isotropically. The
hydrogen atoms of the pentamethylcyclopentadienyl rings were
positioned geometrically and refined by using a riding model.
In a similar treatment to that of 6, all non-hydrogen atoms of 7
were anisotropically refined. All the hydrogen atoms of the imido
and methylene benzyl groups were located in the difference Fourier
map and refined isotropically. The hydrogen atoms of the penta-
methylcyclopentadienyl and phenyl rings were positioned geo-
metrically and refined by using a riding model.
In the case of 9, all non-hydrogen atoms were anisotropically
refined and the hydrogen atoms were positioned geometrically and
refined by using a riding model.
All the non-hydrogen atoms of 13, 15, and 16 were anisotropi-
cally refined. The hydrogen atoms of the imido groups were located
in the difference Fourier map and refined isotropically, while the
rest were positioned geometrically and refined by using a riding
model.
1
5
Me
5
), 12.3 (C
5
Me
5
), not observed AlCH
3
. MS (EI, 70
+
+
eV): m/z (%) 669 (1) [M - 2MeH] , 648 (14) [M - MeH - Cl] ,
+
5
-
Ti
13 (14) [M - MeH - Cl - C
5
Me
5
] , 377 (29) [M - MeH - Cl
+
+
2C
5
Me
5
] , 91 (50) [AlClMe
2
] . Anal. Calcd for C32
H
54AlClN
4
-
3
(M
w
) 700.85): C 54.84, H 7.77, N 7.99. Found: C 54.27, H
7.52, N 6.47.
5
Synthesis of [Me
3
Ge{(µ
3
-N)Ti
3
(η -C
5
Me
5
)
3
(µ-NH)
-N)(µ
(0.30 g, 0.23 mmol), [GeClMe
0.07 g, 0.46 mmol), and toluene (40 mL). After stirring at room
2
(µ
3
-N)}]
(
{
(
16). A 100 mL Schlenk flask was charged with [Li(µ
4
3
-NH) -
2
5
Ti
3
(η -C
5
Me
5
)
3
(µ
3
-N)}]
2
‚C
H
7 8
3
]
temperature for 24 h the solution was filtered and the volatile
components were removed under reduced pressure to afford 16 as
-
1
an orange solid (0.29 g, 88%). IR (KBr, cm ): 3348 (w), 2907
vs), 2855 (s), 2719 (w), 1490 (w), 1433 (m), 1374 (s), 1261 (w),
225 (m), 1065 (w), 1024 (m), 878 (m), 795 (vs), 758 (s), 710
vs), 672 (vs), 645 (vs), 620 (s), 592 (m), 566 (m), 524 (s), 475
(
1
(
(
2
1
w), 451 (m), 413 (m). H NMR (C
H; NH), 2.09 (s, 30H; C
6
D
6
, 20 °C, δ): 14.19 (s br,
), 1.91 (s, 15H; C Me ), 0.31 (s,
). C{ H} NMR (CDCl , 20 °C, δ): 117.5, 117.3 (C
5
Me
5
5
5
1
3
1
9
H; GeMe
3
3
5
-
Me
5
), 12.2, 11.8 (C
5
Me
5
), 7.5 (GeMe
3
). MS (EI, 70 eV): m/z (%):
Acknowledgment. We are grateful to the Spanish MEC
CTQ2005-00238/BQU), Comunidad de Madrid (GR/MAT/
621/2004), and the Universidad de Alcal a´ (CAM-UAH2005/
62) for support of this research.
+
+
+
7
4
26 (3) [M] , 609 (21) [M - GeMe
3
] , 592 (3) [M - C
5
Me
5
] ,
(
0
0
+
+
58 (10) [M - 2C
5
Me
5
] , 320 (22) [M - 3C
5
Me
5
] , 119 (100)
+
[GeMe
3
] . Anal. Calcd for C33
H56GeN
4
Ti
3
(M
w
) 725.04): C
54.67, H 7.79, N 7.73. Found: C 54.69, H 7.72, N 6.87.
X-ray Structure Determination of 6, 7, 9, 13, 15, and 16.
Supporting Information Available: X-ray crystallographic files
in CIF format for complexes 6, 7, 9, 13, 15, and 16. This material
is available free of charge via the Internet at http://pubs.acs.org.
Orange crystals of 6 and 7 were grown in toluene at room
temperature as described in the Experimental Section. Red crystals
of complex 9 and orange crystals of 13, which crystallized with
one molecule of toluene, were obtained from toluene solutions at
40 °C. Finally, orange crystals of 15 and 16 were grown from a
pentane solution at -40 °C. Crystals were removed from the
Schlenks and covered with a layer of a viscous perfluoropolyether
OM060895+
-
(
39) SORTAV. Blessing, R. H. Acta Crystallogr. 1995, A51, 33-38.
(40) Alcock, N. W. Cryst. Comput. 1970, 271.
(
FomblinY). A suitable crystal was selected with the aid of a
(41) Farrugia, L. J. J. App. Crystallogr. 1999, 32, 837-838.
(
42) Sheldrick, G. M. SHELX97, Program for Crystal Structure Analysis
microscope, attached to a glass fiber, and immediately placed in
the low-temperature nitrogen stream of the diffractometer. The
intensity data sets were collected on a Bruker-Nonius KappaCCD
diffractometer equipped with an Oxford Cryostream 700 unit. The
(
Release 97-2); Universit a¨ t G o¨ ttingen: Germany, 1998.
(43) SIR97. Altomare, A.; Burla, M. C.; Camalli, M.; Cascarano, G. L.;
Giacovazzo, C.; Guagliardi, A.; Moliterni, A. G. G.; Polidori, G.; Spagna,
R. J. Appl. Crystallogr. 1999, 32, 115-119.