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Ein stabiles Diaza-silacyclopropan.

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i
I
This manuscript is
to be cited as
Angew. Chem. Suppl.
1982,750-754
Dieses Manuskript ist
zu zitieren als
Angew. Chem. Suppl.
1982,750-754
C Me3
I
Me3Si
SiMe3
+
FZSiCMeg
Me Si
‘N-N
N-N*
-r
Li’
\H
/
Me3C
‘H
’
1 S i
Me3C
0 Verlag Chernie GmbH, D-BB.LO Weinheim, 1982
F
‘
A
i
.
0721-4227/82/04040755102.50/0
Ein stabiles Diaza-silacyclopropan
+
Me Si
3\N-”/
=Me3
Me3Si
‘N-N’
SiMe3
‘/
Me3C
si
Von Johann Hluchy und Uwe Kllngebiel
M‘3S.
SiMe3
Me3C/
‘Li
‘
F
N’
‘H
N-
H/
Der er ste dreiglledrlge, siliciumhaltige Ring, d a s 1-Aza-2, 3-disilaCyclo-
B
-
I
V
pmpan, wurde 1963 von Fink durch eine Pyrolysereaktion erhalten /l/. InMegSi
zwischen gelang die gezielte Bnthese auch anderer SUlcium-Element-Dreiringsysteme /2-4/.
,SiMe3
\N-N
-LiF
SiMe3
/
‘d
Wir berichten nun uber die Herstellung eines 1,Z-Diaza-
Me3@
\C Me 3
3-silacyclopropans.
Das Zwisclienpmdukt A wird nicht isoliert, es re a gie n mit llthiienem N,N’-
Bis(trimethylsily1)hydrazln unter Umlithiie mg Uber da s Lithiumsalz B zum
x Prib.-Doz. O r . U. Kllngebiel, Dr. J. Hluchy
1.2-Diaaa-3-aUaeyclopropan. Bei den von Seyferi e t.a l. untersuchten Cyclo-
Institut f ur Anorganische Chemie d e r UniversitiU
propmen (SUIranen)/2/ bricht in Reaktionen die Si-C-Bindung auf. hie r ist
T a mm annstr ap 4 , 0-3400 G6ttingen
die ge stre c kk N-N-Blndung die %hwachstelle. Reaktionstemperaturen oberhalb +80°C sowls destiilative oder gaschmmatographische Reinigungsversuche
xx Der Deutechen Forschungsgemeinschaft und dem Fonds d e r Chemischen
de s Diaza-silacyclopmpans mhren zur Bildung de s 01-tert-hutyl-bis(trimethy1Industrie danken w ir ftir die Unterstiitzung dl eser Arbeit.
silylaminoj-silans. (Me3SiNH)zsL(CMe3)2-
-
750
-
- 752
Die in kle ine nn Ringsystemen auftmtende starke Hochfeldverschlebung
Fiuorsiiylsubstituierte Hydrazine reagieren mlt metallnrganischen Basen
wle Butyllithium zu Vier- /5/ und Seohsringen /6.7/. Aus dem Oemisch des
asymmetrischen und symmetrlachen fluorsUylaubstltulerren Bla(trimethy1siiylpydrszin gelingt auch die Kreuzdimerlsation zu Ftinfringen
-
d e s Slliciumsignals in den ” S i - N M R - w r e n
wird e b e n f a h im 6WN-Drei-
ring- e a t e m beobachtet /2,4/.
/a/.
&E!L%E:Ep_!c
0.05 mol d e s lithiierten g.3’- B1s~rlmethylsilyl)hydr~ns
gelirst In
100 ml n-Hexan/25 mI THF wird bet 3OoC mit 0.05 mol D i - ~ - b u t y l d i Q u o r SUM ver8eW.t und 5 h be1 dleaer Temperatur geriihrt. Anschliej3end wird kurz
I
+2RLI
I
zum Sedan erhitzt, die LiraungsmiMl i m Vekuum abgezogen und da s Robprndukt bei 0.01 T o r r in e ine r Kuhlfalle elnkondensiert. Die Reinigung des 1,2-
Diaza-3-ailacyelapropsnserfolgt durch mehrmallges Umkristrrllisleren bei
-15OC aus_n-Hexan. Ausbeute 25 g (63 %), Fp. = 12OC; MS (70 eV):
m/s= 316
(12)_M+, 301 (8 ) I_M-CH31+, 259 (100) IM_C4H9J+; ‘H-NMR (in CHZCIZ.
-
TMS int.):&0.13
-d
= -30.73
SiMe3. 1 . 4 1 CMe3; 29S-NMR (in C6F6. TMS int.):
SICMe3, 3.19 m e 3 .
/
\
N
Pi-
‘I
‘
‘iS
-
(11 W. Fink. Helv. Chlm. Acta 79 (1963) 720.
\
N ’
N
/ \
121 D. Seyferth, J
. Organornet. Chem.
-
100 (1975) 237.
I
D. Seyferth, D. C . Annarelli. J. Am. Chem. ps. 9 1 (1975) 2273.
131 R.T
Conlin, P . P . Gaspar, J . Am Chem. ps. 98 (1976) 3715;
Die sperrige Di-ten-butylfluorsilylgruppe erzwixgt in vergleichbarer ReakD. Seyferth, D.C . Annarelli, S.C. Vick,
tion mit lithiiertem N,N’- Bls(trimethyisilyl)hydrazin die Bildung eines Drei-
ringes
-
751 -
-
753
-
98 (1976)
6382.
I41 M. Baudler, H. Jongebloed, 2. Anorg. Allg. Chem. 458 (1979) 9.
151 U. KHngebiel, J. HIuchy, A . Meller, Chem. Ber. 111 (1978) 906.
161 U . Wannagat, H. Niederpriim, Angew. Chem. 70 (1958) 745;
H. Niederpriim, U . Wannagat, 2. Anorg. Allg. Chem. 311 (1961) 270.
171 U. Klingebiel, G . Wendenburg, A. Meller, 2 . NaNrforsch. B32
(1977) 1482,
1
( A S M ~ ~ ) ~ ) -as
. i t s PPN s a l t , PPN = N(PPh3);
1 and i t s
2
AsEt analog
are readily prepared by the reaction of cis3
[PtC12L2] with three equivalents of SnC12, i n acetone. Pertinent NMR
1 (PPN
data for
s a l t ) and
g
6(11gSn) = -67, 6(’95Pt) =
6(13C) = 19.7,
19037 Hz, 2A(119Sn,117Sn) = 17504 Hz;
181 W. Clegg, M. Haase, J. Hluchy,
U. Klingebtel, G . M . Sheldrick
- 79,
1&(195Pt,119Sn) =
p ([D6]-acetone,-
70OC): 6(’lgSn) =
6(195pt) = -5400, 1i(’95~t,119~n) = 19788 ~ z ,2g(119~n,117~n) =
1 and p
18115 Hz. Both
in VorbereiNng
- 4OoC:
(CDC13,
(AsPh4+ s a l t ) are:
- 5364.
are dynamic on the NMR time scale i n Solution.
The observation o f platinum-tin coupling constants i n excess of 15 KHz
seems t o be q u i t e normal for Pt-SnC13 complexes/6/ and the same can be
Eingegangen am 2 9 . Mai 1981 / Z 38 S /
said for 2g(119Sn,117Sn) i n agreement w i t h recent results for
R u ~(sn~~,),f-/g/.
l
Interestingly, i n the related [Pt(SnCl,),(PEt,),]-,
1.
the same structure as
constant, 1g(195Pt,31P)
s i m i l a r t o those for
which we assum has
the platinum-phosphorus one-bond coupling
i s only 1460 H
.I
1 and 2.
when compared t o the values o f 2400
plexes trans-[PtC12(PR3)2]/14’,
The metal NMR parameters are
1g(195Pt,31P)value
This
- 2600 Hz often
i s quite mdest
found i n the com-
and s t i l l much smaller than the 2014 HZ
value found i n the five-coordinate tetradentate chelate coRIp1ex
[Pt(SnC13)(P(o-AsPh2C6H4)$]
i n which phosphorus and t i n
OCCUPY
pseudo
axial positions. This suggests a r e l a t i v e l y weak P t - P bond.
The coordination geometry around platinum i n
1 (see
figure 1) i s a some-
what distorted trigonal bipyramid, with the A s k 3 ligands i n a x i a l positions. The average platinum-tin bond length
-
754
-
-
756
i s 2.602
0.020(1)
8.
This
-
i s s l i g h t l y larger than the average of the equatorial Pt-Sn lengths
zu titieren als
Angew. Chem. Suppl.
1982,755-760
to be cited as
Angew. Chem. Suppl.
1982,755-760
0 Verlag Chemie GmbH. D-8940 Weinheim, 1982
found i n [Pt(SnC13),13-
2.572
8 ’lo’,
but considerably longer than
4. 2.501 8 ””. Interest-
ingly, both
3
and
$
are s t a t i c i n solution on the NMR t i m e scale, i n
t h a t there i s no evidence for SnC13 dissociation. The averaged Pt-As
0721-4227/82/04040822802.50/0
distance i n
A Hovel Anionic Five-Coordinate
T r i s T r i chl orostannatopl a t i num( II)
2.
t h a t for [PtCl(SnC13)(PhC(NH2)=NOH)(PEt3)]
Complex
**
Albert0 Albinati, Ralph NSgeli, Heinz Ruegger and Paul S. Pregosin
Trichlorostannate complexes of platinum( 11) are recognized as useful
hydrogenation and hydrofonylation c a t a l ~ s t s / l - ~ ’ , although the exact
1i s
also quite long, 2.436
c 0.013(2) 8 . when compared t o
the complexes ~ y m - t r a n s - [ P t ~ C l ~ ( A s k2.308
~)~]
(N(CH3)=CH-(p-CH3C,H4)xAsEt3)]
age 2.380
t O.OlO(7)
8,
2.346
R
for
8
‘12/
and =-[PtCl2
The Sn-C1 distances aver-
i n good agreement with the value o f 2.373
found for the equatorial Sn-C1 i n
2.340
8
2.
8
but longer than the average of
2.
composition of the active species i s not clear. I t i s known t h a t the
Given the rather long platinum-tin and platinum-arsenic bond lengths i n
catalyst functions optimally when the r a t i o of t i n t o platinum exceeds
t h i s f i v e coordinate anion and the small 1J(195Pt,31P)
five, and therefore poly(trich1oro)stannate derivatives may be important
PEt3 complex, ligand dissociation i s not completely unexpected. I t i s
value f o r the
intermdiates. We have recently shown t h a t Mno- and bis(trich1orostan-
probable but not certain t h a t a trichlorostannate leaves the coordina-
nato)platinum complexes containing e i t h e r t e r t i a r y phosphane o r arsane
t i o n sphere t o produce the known‘”
ligands are stable i n ~ o l u t i o n / ~ - and
~ / now report the synthesis and
t h i s i s also dynamic i n solution, i t i s d i f f i c u l t t o be exact concerning
characterization of the new five-coordinate tris(SnC13)anion ((Pt(SnC13)3
the nature o f the exchange process. Further studies on these and re-
- ._
* ‘ Priv.-Doz.
lated phosphane and phosphite complexes are i n progress.
Or. P.S.Pregosin,
Dip1.-Chem. H.Ruegger
Laboratorium W r Anorganische Chemie
Experimntal
ETH-Zentrum, UniversitXtstrasse 6, CH-8092 Zurich (Switzerland)
c i ~ - [ P t C l ~ ( A s M e ~(51
) ~ ]mg,
Prof. A.Albinati,
Dip\.-Chem.
R.Ndgeli
I s t i t u t o d i Chimica Fanaceutica dell‘Universita d i Milano
**
[Pt(SnC13)2L2] complex; however, as
0.10 ml) and SnCIZ (57 mg, 0.30 m l ) were
dissolved i n 2 m l acetone. The r e s u l t i n g orange colored solution was
1-20133 Milano ( I t a l y )
then treated w i t h (PPNJC1 dissolved i n 1 m1 mthylene chloride. Eva-
H.R. thanks the ETH for a fellowship.
poration of the solvent t o give an o i l was followed by addition of 3 m l
-
755
-
-
757 -
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