![Page 1: Raphael Berger, Daniel Bojer, Stuart Hayes Benjamin ... · 5 nnnnBuLi Hexan ----nnnnBuSnMe 3333 MeMMeeMe 3333SnCH 2222IIII Dilithiiertes TMEDA Base---2 HI-2 HI HNHHNNHN NH NNHHNH](https://reader031.vdocuments.site/reader031/viewer/2022021821/5b0548967f8b9a5c308b6141/html5/thumbnails/1.jpg)
1
Ungewöhnliche metallierte Kohlenstoff-VerbindungenMetallalkyl-Chemie mit gesättigten N-Heterocyclen
Norbert W. Mitzel
UNIVERSITÄTBIELEFELD
Support:
DFG
Fonds der Chemischen Industrie
Raphael Berger, Daniel Bojer, Stuart Hayes
Benjamin Hellmann, Ina Kamps, Xin Tian,
Ajay Venugopal
![Page 2: Raphael Berger, Daniel Bojer, Stuart Hayes Benjamin ... · 5 nnnnBuLi Hexan ----nnnnBuSnMe 3333 MeMMeeMe 3333SnCH 2222IIII Dilithiiertes TMEDA Base---2 HI-2 HI HNHHNNHN NH NNHHNH](https://reader031.vdocuments.site/reader031/viewer/2022021821/5b0548967f8b9a5c308b6141/html5/thumbnails/2.jpg)
2
α-Metallierte Amine
M —CH2—N
a) D. J. Peterson, J. Organomet. Chem. 1967, 9, 373; b) D. J. Peterson, J. Am. Chem. Soc. 1971, 93, 4027; c) D. J. Peterson,Organomet. Chem. Rev. 1972, A7, 295; M. Kranz, H. Dietrich,
W. Mahdi, G. Müller, F. Hampel, T. Clark, R. Hacker, W. Neugebauer, A. J. Kos, P. v. R. Schleyer, J. Am. Chem. Soc. 1993, 115, 4698;
d) A. Maercker, Lithium Chemistry 1995, 477; e) R. E. Gawley, Q. Zhang, J. Org. Chem. 1995, 60, 5763; f) C. Strohmann, B. C. Abele, Angew. Chem. 1996, 108, 2515; Int. Ed. Engl. 1996, 35,
2378; g) S. V. Kessar, P. Singh, Chem. Rev. 1997, 97, 721; h) C. Bruhn, F. Becke, D. Steinborn, Organometallics 1998, 17, 2124; i) X. Tian, R. Fröhlich, T. Pape, N. W. Mitzel, Organometallics 2005, 24, 5294.
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3
α-Metallierte Amine
RN
R'
H
RN
R'
H
RN
R'
SnR3
RN
R'
SR
RN
R'
H
R N R'
H
BF3R N R'
Li
BF3
RN
R'
Li
RN
R'
Li
RN
R'
Li
R3SnCH2I
RLiF3B . SMe2
RLi
RLi
Li
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P1
N
C
C
Li
C
Li···Li 2.588 - 3.002 Å
LiCH2N(iPr)2
N
C*
C*-N1.524(3) Å
+HN(iPr)2 –[H2N(iPr)2]I+nBuLi –Me3Sn-nBu Me3SnCH2I
Me3SnCH2N(iPr)2LiCH2N(iPr)2
X. Tian, M. Woski, C. Lustig, D. Le Van, R. Fröhlich, K. Bergander, N. W. Mitzel, Organometallics 2005, 24, 82
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5
nnnnBuLiBuLiBuLiBuLiHexanHexanHexanHexan ---- nnnnBuSnMeBuSnMeBuSnMeBuSnMe3333
MeMeMeMe3333SnCHSnCHSnCHSnCH2222IIII
Dilithiiertes TMEDA
BaseBaseBaseBase---- 2 HI2 HI2 HI2 HI
HNHNHNHN NHNHNHNH NNNN NNNN SnMeSnMeSnMeSnMe3333MeMeMeMe3333SnSnSnSn
NNNN NNNN LiLiLiLiLiLiLiLi
Ausb: 78 %farblose Verb.hoch pyrophorunlösl. in Kohlenwasserstoffenzersetzt Ether und THF
13C-CP-MAS-NMR, 10 kHz: 58.2 (CLi), 61.3 (NMe),64.0 (NCH2)
7Li-CP-MAS-NMR, 10 kHz: -1.2, Cq = 220 kHz
EA: �
X. Tian, R. Fröhlich, T. Pape, N. W. Mitzel, Organometallics 2005, 24, 5294
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6
Direkte Deproto-nierung von Aminen
N N
N N
Li
N N
Li
t-BuLi
n-BuLi
F. H. Köhler, N. Hertkorn, J. Blümel, Chem. Ber. 1987, 120, 2081&V. H. Gessner, C. Strohmann,J. Am. Chem. Soc. 2008, 130, 14412
V. H. Gessner, C. Strohmann,Angew. Chem. 2007, 119, 4650
NN
N
Li
J. Arnold, V. Knapp, et al.Dalton Trans. 2002, 3273
N
NN Li
C. Strohmann, V. H. Gessner, ibid. 2007, 119, 8429
NNMe
Li
Me
Me
H. H. Karsch, Chem. Ber. 1995, 29, 483
N N N N
Li Li
t-BuLi
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7
NN
N NN
NLi
Lithiiertes Trimethylhexahydrotriazin (TMTAC) –ein di-amino-substituiertes Carbanion
nBuLiHexan-78°C
Dr. Xin Tian, 2005
32
NN
N·
Ausb.: 84%; EA: �1H-NMR: 1.19, 1.36, 2.17,
3.62, 2.26, 2.2713C-NMR: 27.0, 37.7, 41.8,
82.9, 45.7, 83.47Li-NMR: 0.02
P1R1 = 0.053
Li1
C‘
Li‘
CN
NN
N
N
2.20
2(3)
2.174(3)
2.153(3)
N
H
![Page 8: Raphael Berger, Daniel Bojer, Stuart Hayes Benjamin ... · 5 nnnnBuLi Hexan ----nnnnBuSnMe 3333 MeMMeeMe 3333SnCH 2222IIII Dilithiiertes TMEDA Base---2 HI-2 HI HNHHNNHN NH NNHHNH](https://reader031.vdocuments.site/reader031/viewer/2022021821/5b0548967f8b9a5c308b6141/html5/thumbnails/8.jpg)
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N
N
N
R
OH
Ph
RPh
O
R
OH
Ph
CHON
N
N
Li 2
N
N
N.2. H2O
1.
HCl / H2O
- TMTAC
- CH2O-[MeNH3]Cl
R = Ph 68%R = Me 70%R = H 51%
R = Ph 70%R = Me 58%R = H 76%
D. Bojer, I. Kamps, X. Tian, A. Hepp, T. Pape, R. Fröhlich, N. W. Mitzel, Angew. Chem. 2007, 119, 4254
Ein neuesCorey-Seebach-analogesAcylierungs-Reagenz
Daniel Bojer
![Page 9: Raphael Berger, Daniel Bojer, Stuart Hayes Benjamin ... · 5 nnnnBuLi Hexan ----nnnnBuSnMe 3333 MeMMeeMe 3333SnCH 2222IIII Dilithiiertes TMEDA Base---2 HI-2 HI HNHHNNHN NH NNHHNH](https://reader031.vdocuments.site/reader031/viewer/2022021821/5b0548967f8b9a5c308b6141/html5/thumbnails/9.jpg)
9
NN
NLi2
NN
N·
Me2AlCl
NN
NAlMe2
N NMe2Al N
I. Kamps, 2005
Ein AlMe2-Derivat von TMTAC
Al
N C
Al
N
C
N
C
NC
P1R1 = 0.040
2.038(2) 1.975(2)
2.030(2)
1.552
(2)
1.493(2)
Ausb.: 1.46 g, 79%; CHN�1H NMR: δ -0.26 ppm (s, 12H, AlCH3), 1.39 ppm (s, 2H, AlCH), 1.86 ppm (s, 6H, NCH3), 2.30 ppm (s, 12H,AlCNCH3), 3.24/3.29 ppm (d, 8H, AlCNCH2); 27Al NMR δ 152 ppm (ν½ = 1000 Hz).
![Page 10: Raphael Berger, Daniel Bojer, Stuart Hayes Benjamin ... · 5 nnnnBuLi Hexan ----nnnnBuSnMe 3333 MeMMeeMe 3333SnCH 2222IIII Dilithiiertes TMEDA Base---2 HI-2 HI HNHHNNHN NH NNHHNH](https://reader031.vdocuments.site/reader031/viewer/2022021821/5b0548967f8b9a5c308b6141/html5/thumbnails/10.jpg)
10
NN
NSiMe3
NN
NLi2
NN
N·
Me3SiCl
Silyl- und Stannyl-TMTAC
N
Si NC
N
P1R1 = 0.047m.p. -25°C
I. Kamps, 2005
Ina Kamps
CHN�
NMR in C6D6:1H: δ = 0.15 (s, SiCH3), 1.84 (s, NCH3), 2.44 (s, SiCNCH3), 2.74 (s, SiCH), 2.75/3.49 (dd, SiCNCH2,
2JHH = 10.2 Hz); 13C: δ = -0.5 (SiCH3), 40.0 (NCH3), 42.0 (SiCNCH3), 78.0 (SiCH, 1JCH = 125 Hz), 80.7 (SiCNCH2); 29Si: δ = -0.52;
NN
NSnMe3
Me3SnCl
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N
SiN
Al
N
P21/nR1 = 0.058
NN
NSiMe2
NN
NSiMe2
CH2Li
CH2Me2Al
Silyl-TMTAC-DerivateN
NN
SiMe3
NN
NSiMe3nBuLi
Li
Me2AlCl
I. Kamps, 2007
1.989(3)
1.859(3)
2.053(2)
1H-NMR (CDCl3): -0.93 (s, SiCH3), 0.14 (s, Si-CH2Al), 0.17 (s, AlCH3), 2.18 (s, NCH3), 2.28 (s, SiCNCH3), 2.41 (br, NCH2N), 2.59 (s, SiCH),27Al-NMR (CDCl3): δ = 184.6 (υ½ = 4000 Hz),29Si-NMR (CDCl3): δ = 6.46
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Ein TMTAC-Addukt von MeLi
I. Kamps, 2007
R3R1 = 0.049
LiLi Li
Li
Li
Li
Li
N
N
N
N
C
CC
C
C
C
C
NMR in C6D61H NMR δ = 0.50 (br, LiCH3), 2.14 (s, NCH3), 3.06 (br, NCH2N)13C NMR δ = 5.02 (LiCH3), 40.27 (NCH3), 77.55 (NCH2N)
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13C. Strohmann, V. H. Gessner, Chem. Asian J. 2008, 3, 1929
Postulierter Deprotonierungs-Mechanismus (TMTAC)
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N N
Li
N N
4
4
t-BuLi exc.- t-Bu-H
. [t-BuLi]4
Ein anderes di-amino-substituiertes Carbanion:sind Ringe relevant?
D. Bojer, I. Kamps, X. Tian, A. Hepp, T. Pape, R. Fröhlich, N. W. Mitzel, Angew. Chem. 2007, 119, 4254
Li1‘
C1‘
C1
Li1
C5
C6N2
N1
C4
C3
C4
I4R1 = 0.075
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15
Cokristallisat mit tert-BuLi
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16
In niedrigeren Konzentrationen …
N N
N N
Li
N
N
N N
Li
NLi
N N
Nt-BuLi eq.- t-Bu-H-
2
Ausb.: 66%; IR: 1634;1H NMR: 1.58, 2.04, 2.11, 2.70 (DMDAC), 3.07, 3.81, 5.14, 5.35, 6.35 (MeN(allyl)); 13C NMR: 23.4, 43.0, 54.3, 79.4 (DMDAC), 46, 65, 111, 145 (MeN(allyl)); 7Li NMR: 1.57
D. Bojer, 2006
Li‘
C1
Li
C7
C8
N2
N3
C4C3
C2
N1
C10
C9
1.301
(3)
2.01
0(3)
1.984(3)
2.206(2)
P1R1 = 0.053
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17
Ein lithiiertes Fünfring-Aminal
N N
Li
N N
N N
2
3
t-BuLi- t-Bu-H
.
I. Kamps,2008
Ausb.: 3.57 g, 45 %; CHN�1H NMR δ 2.26, 2.28, 2.82; 2.65, 2.74, 3.18;
13C NMR 40.3, 54.7, 80.1; 41.0, 59.7; 7Li NMR: 0.26 ppm.
Li‘
C1Li
C6
C8
N2N3
C3C2
N1
C7
N4 P1R1 = 0.057
2.073
2.185(2)
2.173(2)
2.184(2)
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UnterschiedlicheMechanismen?
H. H. Karsch, 1995
N NN N
Li
N N
Li
bzw.t-BuLi
N N
Li
N N
t-BuLi
N N
N
N N
N
Li
t-BuLi orn-BuLi
N N N N
Li Lit-BuLi
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19
Ein mechanistischer Vorschlag für den Sechsring
Dr. Raphael J. F Berger, 2009
RI-DFT(B88-P86)/SV(P)
N
N
CH3
Li
Li
CMe3Me3C
H
H
H
H
ν = 74 cm-1
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20
Übergangszustand für dieDeprotonierung des Sechsrings
Stuart A. Hayes, 2009
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21Raphael J. F Berger, 2009
N
N
C
Li
Li
CMe3C
H
H H
H
H
H
H
Me3
RI-DFT(B88-P86)/SV(P)
ν = 54 cm-1
Ein mechanistischer Vorschlag für den Fünfring
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22
Übergangszustand für dieDeprotonierung des Fünfrings
Stuart A. Hayes, 2009
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23Raphael J. F Berger, 2009 RI-DFT(B88-P86)/SV(P)
ν = 129 cm-1
Me3Me3
C
N
N
Li
Li CC
H
HCH3
C
H
HH
H
H
H
Mechanistischer Vorschlag - offenkettiges Aminal
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24Raphael J. F Berger, 2009 RI-DFT(B88-P86)/SV(P)
ν = 54 cm-1
C
NN
C
Li
Li
CMe3Me3C
H
HHH
HH
HH
Mechanistischer Vorschlag - offenkettiges Aminal
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25
Übergangszustand für dieDeprotonierung des offenkettigen Aminals
Stuart A. Hayes, 2009
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26
N N NN
Li Li
N N NN
Li Li
N N NN
t-BuLi
Zwei di-amino-substituierte Carbanionenin einem Molekül
Ausb.: 84 %; 1H NMR 1.30, 2.07, 2.30, 2.32 (LiCH), 2.80, 3.05 (NCH2N); 13C NMR 27.6, 47.4, 52.5, 59.2, 77.0 (NCH2N), 93.1 (LiCH). 7Li NMR 0.98. CHN�
NC
LiN
Li
N
C
NLi
Li
C C
C
C
C
C
I. Kamps, 20082.
149
2.04
5
2.221
2.167
P421/cR1 = 0.030
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27
N N NN
LiLiLi
N N NN
C
N N NN
Me3
tBuLi - tBuH
Zwischenprodukt der Lithiierung
C···H 3.084 ÅI. Kamps, 2009
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N N NN
YLi
Y
N N NN
Li
ClCl
N N NN
Li Li
N N NN
Li Li
CpYCl2 - LiCl
Ein Selten-Erd-Derivat
Y
N
N
Li
LiP21/nR1 = 0.024
N
N
N
NN
N
Y
Cl
Cl
Benjamin Hellmann, Ina Kamps, 2009
Ausb. 13%; NMR: 1H �, 13C �, 7Li: -0.1CHN: gef (ber) C 47.34 (47.25), H 6.69 (6.66), N (13.55) 13.78
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29
Me3
Me3
N N
N
N
N
N
N N
N N
N
N
N
N
N N
Li LiLi
Li
N N
N
N
N
N
N N
AlAlY
MeY(AlMe4)3
tBuLi
- CH4
Heterometallische Synergie als Deprotonierungs-Stategie
Daniel Bojer, Ina Kamps, 2008
Y
C
N
N
C
N
C
N
C
Al
N
N N
Pca21R1 = 0.066Al
![Page 30: Raphael Berger, Daniel Bojer, Stuart Hayes Benjamin ... · 5 nnnnBuLi Hexan ----nnnnBuSnMe 3333 MeMMeeMe 3333SnCH 2222IIII Dilithiiertes TMEDA Base---2 HI-2 HI HNHHNNHN NH NNHHNH](https://reader031.vdocuments.site/reader031/viewer/2022021821/5b0548967f8b9a5c308b6141/html5/thumbnails/30.jpg)
30
N NN
[La{Al(CH3)4}3]N N
N
LaC CH3
AlAl
CH3
CH3
CC
Al
CH3CH3
CH3CH3
C
+- CH4
H2
H3
H3H3
TMTAC
Daniel Bojer, 2008; Dalton Trans. im Druck
Ausb: 66%. NMR: 1H: –1.22 (s, br, Al(CH3)4), –0.93 (s, br, Al(CH3)3), –0.76 (s, br, Al2CH2), 2.42 (s, NCH3), 3.03 (d, 2JHH = 8.9 , N2CH2), 4.10 (d, 2JHH = 8.9, N2CH2);
13C{1H}: –10.2 (s, br, Al(CH3)4), –5.5 (s, vbr, Al2CH2), –1.3 (s, br, Al(C-
H3)3), 39.0 (s, NCH3), 77.0 (s, N2CH2); 27Al: 153 (s, Al(CH3)3), 183 (s, Al(CH3)4); CHN �.
TMTAC / Ln(AlMe4)3 großes Ln3+-Ion: La
La
N
Al
C
AlAl
N N
C
C
C
C
C
C
CC
C
C
![Page 31: Raphael Berger, Daniel Bojer, Stuart Hayes Benjamin ... · 5 nnnnBuLi Hexan ----nnnnBuSnMe 3333 MeMMeeMe 3333SnCH 2222IIII Dilithiiertes TMEDA Base---2 HI-2 HI HNHHNNHN NH NNHHNH](https://reader031.vdocuments.site/reader031/viewer/2022021821/5b0548967f8b9a5c308b6141/html5/thumbnails/31.jpg)
31R. Litlabo, M. Zimmermann, K. Saliu, J. Takats, K. W. Törnroos, R. Anwander, Angew. Chem. Int. Ed. 2008, 47, 9560
Ein ähnliches Produkt aus [La(AlMe4)3] induziertdurch einen anionischen tripodalen Liganden
![Page 32: Raphael Berger, Daniel Bojer, Stuart Hayes Benjamin ... · 5 nnnnBuLi Hexan ----nnnnBuSnMe 3333 MeMMeeMe 3333SnCH 2222IIII Dilithiiertes TMEDA Base---2 HI-2 HI HNHHNNHN NH NNHHNH](https://reader031.vdocuments.site/reader031/viewer/2022021821/5b0548967f8b9a5c308b6141/html5/thumbnails/32.jpg)
32
N NN
M
C CMe2Al AlMe2
CC
Al
C C
MCCH3
Me2AlAlMe2
CC
Al
C C
H
NN
N
N NN
MCCH3
Me2AlAlMe2
C
Al
C C
N NN
MCCH3
Me2AlAlMe2
CAl
C C
H
Me2
Me2 Me2
H3
H3
H3
H3
H3
H3
H3
H3
H2
H3
H3
H3
H3
H2H3
H2
H3
H2
H3
A
B
C D (M = La)
a
b
c
- CH4
Mechanistischer Vorschlag: Bisaluminat
![Page 33: Raphael Berger, Daniel Bojer, Stuart Hayes Benjamin ... · 5 nnnnBuLi Hexan ----nnnnBuSnMe 3333 MeMMeeMe 3333SnCH 2222IIII Dilithiiertes TMEDA Base---2 HI-2 HI HNHHNNHN NH NNHHNH](https://reader031.vdocuments.site/reader031/viewer/2022021821/5b0548967f8b9a5c308b6141/html5/thumbnails/33.jpg)
33
4 Sm(AlMe4)3 + 4 TMTAC
[Sm3(µ6-C)(TMTAC)(AlMe3)3(CH2AlMe3)(Me)]*
+ [Sm(TMTAC)(Me3AlCH2AlMe2CH2AlMe3)]
+ [(TMTAC)(AlMe3)2]
+ 7 CH4
*analog für Y(AlMe4)3
Überraschung mit TMTAC
Ina KampsAjay Venugopal
2007/8
NN
N
![Page 34: Raphael Berger, Daniel Bojer, Stuart Hayes Benjamin ... · 5 nnnnBuLi Hexan ----nnnnBuSnMe 3333 MeMMeeMe 3333SnCH 2222IIII Dilithiiertes TMEDA Base---2 HI-2 HI HNHHNNHN NH NNHHNH](https://reader031.vdocuments.site/reader031/viewer/2022021821/5b0548967f8b9a5c308b6141/html5/thumbnails/34.jpg)
34
- - -
Ajay Venugopal,Ina Kamps,Alexander Willner2007Dalton Trans. im Druck
N NN
[Sm{Al(CH3)4}3]+
- CH4TMTAC
+ [Sm3(µ6-C)(TMTAC)(AlMe3)3(CH2AlMe3)(Me)]P21/m, R = 0.038
TMTAC / Ln(AlMe4)3 mittleres Ln3+-Ion: Sm
-
Pna21, R = 0.054
Sm
N
Al
N
N
AlAl
C C
Al CH2
Al CH2
Al
CH3
CH3CH3
CH3 CH3
CH3
CH3CH3
![Page 35: Raphael Berger, Daniel Bojer, Stuart Hayes Benjamin ... · 5 nnnnBuLi Hexan ----nnnnBuSnMe 3333 MeMMeeMe 3333SnCH 2222IIII Dilithiiertes TMEDA Base---2 HI-2 HI HNHHNNHN NH NNHHNH](https://reader031.vdocuments.site/reader031/viewer/2022021821/5b0548967f8b9a5c308b6141/html5/thumbnails/35.jpg)
35
N N
N
MCCH3
Me2AlAlMe2
C
Al
C
N NN
MCCH3
Me2Al AlMe2C
Al
C
Me2
Me2
N NN
MCCH3
Me2AlAlMe2
CAl
C C
H
Me2
H2
H3
H2
- CH4
H2
H3
H2
E
F (M = Sm)
d
e
H2
H3
H2
H3
D
Mechanistischer Vorschlag: Trisaluminat I
![Page 36: Raphael Berger, Daniel Bojer, Stuart Hayes Benjamin ... · 5 nnnnBuLi Hexan ----nnnnBuSnMe 3333 MeMMeeMe 3333SnCH 2222IIII Dilithiiertes TMEDA Base---2 HI-2 HI HNHHNNHN NH NNHHNH](https://reader031.vdocuments.site/reader031/viewer/2022021821/5b0548967f8b9a5c308b6141/html5/thumbnails/36.jpg)
36
[Y3(µ6-C)(TMTAC)(AlMe3)3(CH2AlMe3)(Me)]
Ajay VenugopalIna KampsAlexander Willner2007
Y1-C33 2.697(4)
Y2-C33 2.440(3)
Al1-C33 2.040(3)
Al3-C33 2.076(4)
Y1-C24 2.458(3)
Al2-C24 2.051(3)
Al2-C23 2.084(4)
Y2-C24 2.367(3)
Y2-C40 2.511(4)
Yield: 85% IR ν = 1263 (s), 1210 (s), 1167 (w), 1099 (w), 1012 (s), 941 (s), 719 (w), 681 (w). CHN �
P21/m, R1 = 0.055
TMTAC / Ln(AlMe4)3 mittleres Ln3+-Ion: Sm > Y
N
C
Al
NN
Al
Al
C
Al
Al
CY Y
analog: [Sm3(µ6-C)(TMTAC)(AlMe3)3(CH2AlMe3)(Me)], R1 = 0.033
C Y
![Page 37: Raphael Berger, Daniel Bojer, Stuart Hayes Benjamin ... · 5 nnnnBuLi Hexan ----nnnnBuSnMe 3333 MeMMeeMe 3333SnCH 2222IIII Dilithiiertes TMEDA Base---2 HI-2 HI HNHHNNHN NH NNHHNH](https://reader031.vdocuments.site/reader031/viewer/2022021821/5b0548967f8b9a5c308b6141/html5/thumbnails/37.jpg)
37
N NN
MCCH3
Me2AlAlMe2
CAl
C C
H
Me2
N NN
MC CH3
Me2AlAlMe2
CMe2Al
CH
N NN
MC
CH3
AlAlMe2
C
AlC
H
Me2
Me2
H2
H3
H2
H3
D H3
H3
H3
H3
G
H
f
- CH4
Sm
N
CAl
N N
Al
CC
C
H
Mechanistischer Vorschlag: isomeres Trisaluminat II
Daniel Bojer, 2009
P21/c,
R = 0.033
Sm-C 2.340(2) Å
AnalogesCyclohexyl-System
![Page 38: Raphael Berger, Daniel Bojer, Stuart Hayes Benjamin ... · 5 nnnnBuLi Hexan ----nnnnBuSnMe 3333 MeMMeeMe 3333SnCH 2222IIII Dilithiiertes TMEDA Base---2 HI-2 HI HNHHNNHN NH NNHHNH](https://reader031.vdocuments.site/reader031/viewer/2022021821/5b0548967f8b9a5c308b6141/html5/thumbnails/38.jpg)
38
N NN
MC
CH3
AlAl
CH3
C
Al CH3
C
H
N
NN
M
C
CH3
Al
Al
C
Me2Al
C
C
N NN
MC
CH3
Al
Al
C
AlC
H
C
M
C
CH3
AlMe2
N
N
N
Me3Al
Me3AlCH3
CH3
Me2
Me2
Me2
N NN
MC
CH3
Al
Al
C
AlC
H
C
M
C
CH3
AlMe2
CH3
CH3
Me2
Me2
N NN
AlMe3 AlMe3
Me2
Me2
Me2
H3
H3
H3
H3H2
H3
H3
H3
H3
H2
H
I
H3
H3
H3
H2
J
D
i
h
+
Mechanistischer Vorschlag: mehrkernigeCarben-KomplexeTrisaluminat II
Bisaluminat
![Page 39: Raphael Berger, Daniel Bojer, Stuart Hayes Benjamin ... · 5 nnnnBuLi Hexan ----nnnnBuSnMe 3333 MeMMeeMe 3333SnCH 2222IIII Dilithiiertes TMEDA Base---2 HI-2 HI HNHHNNHN NH NNHHNH](https://reader031.vdocuments.site/reader031/viewer/2022021821/5b0548967f8b9a5c308b6141/html5/thumbnails/39.jpg)
39
N NN
MC
CH3
Al
Al
C
AlC
C
MC
AlMe2
CH3
CH3
Me2
Me2
N NN
MC
C
Al
Al
C
AlC
C
MC
AlMe2
CH3 CH2
C
MC
CH3
AlMe2Me2
Me2
N NN
MC
C
Al
Al
C
AlC
C
MC
AlMe2
CH3 CH2
C
MC
CH3
AlMe2Me2
Me2
N NN
MC
CH3
Al
Al
C
AlC
H
C
M
C
CH3
AlMe2
CH3
CH3
Me2
Me2
K
H3
H3
H3
H2
H3
H3
H3
H2
H3
H2
H3
L
H3
H3
H3
H2
H3
H2
H3
(M = Y, Sm)
+ C
analog h
analog i
M
- 2 k
H3
H3
H3
H2
J
i
- CH4
![Page 40: Raphael Berger, Daniel Bojer, Stuart Hayes Benjamin ... · 5 nnnnBuLi Hexan ----nnnnBuSnMe 3333 MeMMeeMe 3333SnCH 2222IIII Dilithiiertes TMEDA Base---2 HI-2 HI HNHHNNHN NH NNHHNH](https://reader031.vdocuments.site/reader031/viewer/2022021821/5b0548967f8b9a5c308b6141/html5/thumbnails/40.jpg)
40
CH3-, CH2- und C-Komplex
N
C
Al
NN
Al
Al
C
Al
Al
CY Y
C Y
![Page 41: Raphael Berger, Daniel Bojer, Stuart Hayes Benjamin ... · 5 nnnnBuLi Hexan ----nnnnBuSnMe 3333 MeMMeeMe 3333SnCH 2222IIII Dilithiiertes TMEDA Base---2 HI-2 HI HNHHNNHN NH NNHHNH](https://reader031.vdocuments.site/reader031/viewer/2022021821/5b0548967f8b9a5c308b6141/html5/thumbnails/41.jpg)
41
27Al: 154 ppmY-CH3: 1H-NMR -0.83 (2JYH = 1.7 Hz)
13C-NMR: 14.1, 89Y-NMR 740
TCYTAC + Y(AlMe4)3 →
[(TCYTAC)2YMe2]+ [AlMe4]-
+ (TCYTAC)(AlMe3)2
Ein Heterocyclus mit sperrigeren Substituenten:YMe2-Kationen
Daniel Bojer, 2008
YC2
N6
C1
N5
C
N4
N1
N2
Al
N3
![Page 42: Raphael Berger, Daniel Bojer, Stuart Hayes Benjamin ... · 5 nnnnBuLi Hexan ----nnnnBuSnMe 3333 MeMMeeMe 3333SnCH 2222IIII Dilithiiertes TMEDA Base---2 HI-2 HI HNHHNNHN NH NNHHNH](https://reader031.vdocuments.site/reader031/viewer/2022021821/5b0548967f8b9a5c308b6141/html5/thumbnails/42.jpg)
42
TCYTAC + Sm(AlMe4)3 →
[(TCYTAC)2Sm(AlMe3)2] +½ C2H6 + AlMe3
+ [(TCYTAC)Sm{CH(AlMe3)3}]
Daniel Bojer, 2008
PnR1 = 0.043
Sm
C
N2
N1
C
N4Al2
Al1
N6
N5
N3
Ein Heterocyclus mit sperrigeren Substituenten:sterisch induzierte Reduktion
+II
+III
+III
![Page 43: Raphael Berger, Daniel Bojer, Stuart Hayes Benjamin ... · 5 nnnnBuLi Hexan ----nnnnBuSnMe 3333 MeMMeeMe 3333SnCH 2222IIII Dilithiiertes TMEDA Base---2 HI-2 HI HNHHNNHN NH NNHHNH](https://reader031.vdocuments.site/reader031/viewer/2022021821/5b0548967f8b9a5c308b6141/html5/thumbnails/43.jpg)
43
Sterisch induzierte Reduktion
C. Ruspic, S. Harder Angew. Chem 2008, 120, 2151. Siehe auch: W. J. Evans, B. L. Davis, T. M. Champagne, J. W. Ziller Proc. Nat. Acad. Sci. 2006, 103, 12678
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44
Zusammenfassung
N N
Li
N N
RLi
NN
Li
LiC
CMe3
H
H
Me3
Einfache aber selektive Deprotonierung von
Ring-Aminalen
N NN
[M{Al(CH3)4}3]
N NN
M
+
- CH4
Heterocyclen-induzierteMethylgruppen-Degradation
in Al(CH3)4-Verbindungen
kondensierteCH2-, CH- and C-Einheiten
![Page 45: Raphael Berger, Daniel Bojer, Stuart Hayes Benjamin ... · 5 nnnnBuLi Hexan ----nnnnBuSnMe 3333 MeMMeeMe 3333SnCH 2222IIII Dilithiiertes TMEDA Base---2 HI-2 HI HNHHNNHN NH NNHHNH](https://reader031.vdocuments.site/reader031/viewer/2022021821/5b0548967f8b9a5c308b6141/html5/thumbnails/45.jpg)
45
Benjamin
Hellmann
Beate
Neumann
Dr. Stuart
Hayes
Constantin
Sicking
Missing:
Britta Rummel
Ulf Strasser
Ina
Kamps
Jasmin
Chmiel
Dr. Ajay
Venugopal
Daniel
Bojer
Prof.
Peter Jutzi
Joseph
Izundu
Dr. Andreas
Mix
Dr. Kinga
Leszczynska
Michael
Hagemann
Daniel
Meissner
Roswitha
Becker
Matthias
Hülsmann
Verena
Orth
Daniel
Winkelhaus
Dr. Raphael
Berger
Alexander
Willner
Hans-Georg
Stammler