Phenylene-Bridged Organolanthanide Complexes
Organometallics, Vol. 28, No. 8, 2009 2427
5
Synthesis of p-bis{η -(2,3,4,5-tetramethylcyclopentadienyl)-
La[N(SiHMe
the mixture was cooled to room temperature, concentrated HCl (15
mL) was added dropwise and this mixture was refluxed for 2 h.
After it was cooled, the solution was filtered and the collected white
solid washed with additional ethanol (10 mL). Solvent was removed
from the combined ethanol filtrates in vacuo to give an off-white
solid, which was then redissolved in concentrated aqueous KOH
(30 mL). The mixture was extracted with 50 mL of ether three
times. The combined ether extracts were washed with 30 mL of
2 2 2 2 2 3
) ] }phenylene (6). A solution of La[N(SiHMe ) ]
800 mg, 1.5 mmol) and p-bis(2,3,4,5-tetramethylcyclopentadi-
(
enyl)phenylene (238 mg, 0.7 mmol) in dry pentane (60 mL) under
Ar was stirred for 2 days. Complex 6 was isolated by crystallization
from the reaction mixture at -30 °C to afford 550 mg (66% yield)
of pale yellow microcrystals. IR (Nujol, cm ): 2108 sh, 2054 br
s, 1995 br s, 1874 br s, 1745 m, 1660 w, 1602 w, 1520 s, 1247 vs,
-
1
1
068 s, 1021 w, 894 vs, 835 vs, 787 s, 761 s, 690 m, 629 m, 599 m.
2 4
saturated aqueous NaCl and then dried over Na SO . The ether
1
H NMR (500 MHz, C
J
6
D
6
, 25 °C): δ 7.66 (s, 4H, C
SiH ) 144 Hz, 8H, SiHMe ), 2.38 (s, 12H, C Me ), 2.24 (s, 12H,
). C NMR (125 MHz,
, 25 °C): δ 134.6, 130.0, 127.4, 123.3, 121.4, 12.3, 11.3, 2.3.
Si La : C, 42.76; H, 7.54; N, 4.99. Found:
6
H
4
), 4.83 (m,
solution was filtered and the solvent removed in vacuo to give a
pale yellow oil. The product was purified by distillation in a
Kugelrohr apparatus at ∼10 mTorr with an oven temperature of
1
2
5
13
4
3
C
C
5
Me
4
), 0.25 (d, JHH ) 3 Hz, 48H, SiHMe
2
1
D
6
45 °C to give 0.77 g (23% yield) of 33 as a colorless liquid. H
6
Anal. Calcd for C40
C, 42.14; H, 7.60; N, 4.60.
H
84
N
4
8
2
NMR (500 MHz, C
(m, 2H, CHdCH ), 2.47 (t, J ) 7 Hz, 2H, H
7 Hz, 2H, CH CHdCH ), 1.31-1.17 (m, 8H, CH
br, 2H, NH , 25 °C): δ 139.3, 114.5,
). 13C NMR (100 MHz, C
6
D
6
, 25 °C): δ 5.79 (m, 1H, CHdCH
NCH ), 1.97 (q, J )
CH CH ), 0.59
2
), 5.02
2
2
2
5
2
2
2
2
2
Synthesis of (η -phenyltetramethylcyclopentadienyl)La[N-
(
2
6 6
D
(
SiHMe
mmol) in dry pentane (20 mL) was added a solution of 4 in pentane
2.0 mL, 0.5 M, 1.0 mmol). The reaction mixture was stirred under
2 2 2 2 2 3
) ] (9). To a solution of La[N(SiHMe ) ] (536 mg, 1.0
4
2.6, 34.3, 34.2, 29.4, 29.3, 27.1. MS (m/z (relative abundance)):
[
(
(
(
M + 1]+ 128 (3), [M - 1]+ 126 (1), 112 (4), 98 (7), 95 (3), 87
(
4), 86 (86), 84 (27), 82 (9), 81 (9), 70 (17), 69 (19), 67 (21), 56
69), 55 (24), 54 (19), 53 (17), 45 (24), 41 (100), 39 (89). HRMS
m/z): [M ] calcd for C
Ar for 2 days, and then all volatiles were removed in vacuo to
yield crude 9 as a viscous yellow oil. The crude product is
approximately 70-80% pure and contains no unreacted La[N(Si-
HMe
+
8
H17N 127.1361, found 127.1348.
1
Synthesis of N-(But-3-enyl)-1,3-diaminopropane (34). To a
2
)
2
]
3
or 4 ( H NMR assay). Repeated purification attempts via
flask containing 1,3-diaminopropane (8.2 mL, 99 mmol) at 60 °C
was added dropwise 4-bromobut-1-ene (1.0 mL, 9.9 mmol), and
the mixture was stirred at 60 °C overnight. After the mixture was
recrystallization from an exhaustive array of solvents, sublimation,
or Ph PdO complexation were unable to separate the unidentified
impurities from the extremely lipophilic 9. H NMR (500 MHz,
, 25 °C): δ 7.45 (m, 2H, Ph), 7.34 (m, 2H, Ph), 7.11 (m, 1H,
Ph), 4.78 (m, 4H, SiHMe ), 2.29 (s, 6H, C Me ), 2.22 (s, 6H,
), 0.21 (d, JHH ) 2.5 Hz, 24H, SiHMe ).
Synthesis of p-bis{η -(2,3,4,5-tetramethylcyclopentadienyl)-
3
1
cooled to room temperature, CH
mixture was washed four times with 50 mL of water. The mixture
was then dried over MgSO and filtered, and the solvent was
2 2
Cl was added (100 mL) and this
6 6
C D
2
5
4
3
4
C
5
Me
4
2
carefully removed in vacuo at 0 °C to give a pale yellow oil. The
product was purified by vacuum-transferring it away from the
nonvolatile impurities to give 50 mg (4% yield) of 34 as a colorless
5
2
La[K -(NSiHMe
10). In an attempt to generate Nd[N(SiHMe
Nd[N(TMS) (1.00 g, 1.6 mmol) in dry pentane (50 mL) was
2
)(HNSiHMe
2
)SiMe
2
2 2
][N(SiHMe ) ]}phenylene
(
2
)
2
]
3
, to a solution of
24
oil. NMR and mass spectral data agree with the literature values.
2 3
]
Synthesis of N-(But-3-enyl)-1,4-diaminobutane (35). To a flask
containing 1,4-diaminobutane (10 mL, 99 mmol) at 60 °C was
added dropwise 4-bromobut-1-ene (1.0 mL, 9.9 mmol), and the
mixture was stirred at 60 °C overnight. After the mixture was cooled
added excess 1,1,3,3-tetramethyldisilazane (12 mL, 68 mmol). This
reaction was allowed to proceed over a period of 2 weeks, during
which time a small amount of air was inadvertently introduced into
3+
the reaction vessel, resulting in a mixture of Nd species containing
the bidentate ligand N,N′-bis(dimethylsilyl)-1-amino-1,1-dimeth-
ylsilylamide. After removal of volatiles in vacuo, the resulting
viscous blue oil was reacted with 6 (233 mg, 0.2 mmol) in dry
pentane (50 mL) under Ar for 1 h. Crystallization from the reaction
mixture at -30 °C afforded 215 mg of colorless block crystals of
to room temperature, CH
was washed four times with 50 mL of water. The mixture was then
dried over MgSO and filtered, and the solvent was removed in
2 2
Cl was added (100 mL) and this mixture
4
vacuo at 0 °C to give a pale orange oil. The product was purified
by vacuum-transferring it away from the nonvolatile impurities to
1
give 220 mg (16% yield) of 35 as a colorless oil. H NMR (500
10 coated with a small amount of pale blue oil. These crystals were
MHz, C
CHdCH
CH CHdCH
NH). C NMR (100 MHz, C
6
D
2
6
, 25 °C): δ 5.77 (m, 1H, CHdCH
), 2.55-2.43 (m, 6H, NCH ), 2.14 (q, J ) 7 Hz, 2H,
), 1.39-1.29 (m, 4H, CH CH CH ), 0.49 (br, 3H,
, 25 °C): δ 137.4, 115.9, 50.1,
2
), 5.04 (m, 2H,
used for the X-ray crystal structure determination of 10, and
subsequent recrystallization from pentane to remove the pale blue
coating oil only recovered 30 mg (11% yield) of the crystals. Owing
2
2
2
2
2
2
1
3
6
D
6
+
to the minimal yield, analysis beyond that reported below was not
4
9.5, 42.6, 35.1, 32.1, 28.0. HRMS (m/z): [M ] calcd for C
42.1470, found 142.1464.
Synthesis of 7-Octyn-1-amine (36). To a solution of 7-octyn-
8 18 2
H N
1
performed. H NMR (500 MHz, C
D
6 6
, 25 °C): δ 7.66 (s, 4H, C
)(HNSiHMe )SiMe ]), 4.92 (m, 4H,
), 4.78 (m, 2H, [(NSiHMe )(HNSiHMe )SiMe ]), 2.45
Me ), 2.34 (s, 12H, C Me ), 0.33 (m, 48H, SiMe), 0.02
d, JHH ) 2.5 Hz, 12H, [(NSiHMe )(HNSiHMe
125 MHz, C , 25 °C): δ 134.5, 130.1, 127.5, 123.2, 120.5, 12.6,
1.6, 5.5, 3.0, 0.5.
6 4
H ),
1
5
.11 (m, 2H, [(NSiHMe
2
2
2
N(SiHMe
)
2 2
2
2
2
1-ol (2.5 g, 20 mmol) and triethylamine (3.3 mL, 24 mmol) in dry
(
(
(
s, 12H, C
5
4
5
4
CH Cl (25 mL) at 0 °C was added dropwise methanesulfonyl
2
2
3
13
2
2
)SiMe
2
]). C NMR
chloride (2.0 mL, 26 mmol). The mixture was slowly warmed to
room temperature, stirred overnight, and then poured into 100 mL
of H O. The aqueous phase was extracted with 30 mL of CH Cl
2
6 6
D
1
2
2
Synthesis of 7-Octen-1-amine (33). A suspension of 8-bromo-
-octene (5.00 g, 26.2 mmol) and potassium phthalimide (5.33 g,
8.8 mmol) in dry DMF (60 mL) was heated at 60 °C for 24 h.
four times, and the combined organic portions were washed with
100 mL of saturated aqueous NaCl. The CH Cl solution was dried
1
2
2
2
over MgSO and filtered, and the solvent was removed from the
4
The resulting cloudy pale yellow mixture was cooled to room
temperature and then filtered. The filtrate was added to 50 mL of
filtrate in vacuo to give a dark orange oil. The oil was then filtered
through a pad of silica, the silica was washed with 200 mL of 1/1
hexanes/ether, and the solvent removed from the combined filtrate
in vacuo to give a pale yellow oil. This oil was then redissolved in
dry THF (50 mL), and LiCl (1.26 g, 30 mmol) was added. The
mixture was refluxed overnight, and then after it was cooled to
room temperature, it was poured into 100 mL of saturated aqueous
5
0/50 saturated NaCl/H
times. The combined ether extracts were washed with 20 mL of
saturated aqueous NaCl and then dried over K CO . The ether
2
O and extracted with 30 mL of ether three
2
3
solution was filtered and the solvent removed in vacuo to give
N-oct-7-enylphthalimide as a pale yellow liquid. Without further
purification, the N-oct-7-enylphthalimide was redissolved in ethanol
(
2
40 mL). To this solution was added hydrazine hydrate (1.3 mL,
6.8 mmol), and the mixture was heated at 60 °C overnight. After
(
24) Bergmann, D. J.; Campi, E. M.; Jackson, W. R.; McCubbin, Q. J.;
Patti, A. F. Tetrahedron 1997, 53, 17449–17460.