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Ionization Isomerism of Sulfinato Complexes of Transition Metals.

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over, in the spectrum of the reaction H Q f 0 2 , the 515-nm
band is twice as strong as the 568-nm band. Since the rate of
reaction of 0 2 with HQ, having two -0- groups, must
statistically be twice as high as that of 0 2 with SQ, having
one -0- group, the same relationship is to be expected between the intensities of the emission bands.
phine sulfide are not formed, even on heating with an excess
of SO2 at 185 'C for 8 days.
Compounds ( l a ) and (16) react with SeOz in boiling benzene
to give the phosphine oxide and either selenium or the phosphine selenide, depending on the relative proportions of the
reagents.
Since the singlet states of anthraquinonesulfonate lie at 260
SQ* and Q* must be triplet
states. This means that removal of an electron from a group
2 ( l a , b)
(new*) and 320nm (n+n*),
like
>k-O:@ leaves
considerably lower energy required for its formation (49
instead of 88 kcaljmole), the antibonding state should be a
triplet state which undergoes transition into the singlet
ground state in a subsequent step, thereby emitting a very
small portion of its energy as light.
Received: January 30, 1970
[ Z 164 IE]
German version: Angew. Chem. 82, 321 (1970)
[ * ] Prof. Dr. J. Stauff and P. Bartolmes
Institut fur Physikalische Biochemie und Kolloidchemie
der Universitat
6 Frankfurt/Main 1, Robert-Mayer-Strasse 11 (Germany)
[l] 1. Stauff and F. Nimmerfall, 2. Naturforsch. 246, 852
(1969).
[2] K . D . Gundermann: Chemilumineszenz organischer Verbindungen. Springer, Berlin 1968.
Reactions of Tritolylphosphines
By S. I. A . El Sheikh, B. C. Smith,and M . E. Soheir[*]
Tri-p- ( l a ) and tri-m-tolylphosphine ( I b ) resemble triphenylphosphine in their oxidation behavior, whereas tri-o-tolyphosphine ( I c ) differs in its reactions with several oxidizing
agents. Thus ( l a ) and ( I b ) react with thionyl chloride in
boiling benzene t o give the phosphine oxide and disulfur dichloride [ I ] .
The initially formed triaryldichlorophosphorane undergoes
subsequent conversion into the phosphine oxide. Under
similar conditions ( I c ) gives a mixture of the phosphine
oxide and phosphine sulfide.
( l a ) and (16) recrystallize unchanged from liquid sulfur dioxide, but undergo oxidation when the yellow solutions are
heated in sealed tubes (185 OC/2 days):
+ SO2
+ Se02
2 R3PO+ Se
--f
+ 2 R 3 P O + R3PSe
the >C=O group not in the bonding
z state but initially in the antibonding x* state. Owing to the
3 (la, 6)
3 (la, 6)
+ SeO2
+ 2 R3PO
+ R3PS
The phosphine ( I c ) does not react under these conditions.
Received: February 2, 1970
[ Z 165 IE]
German version: Angew. Cheni. 82,326 (1970)
-~
-
[*I Dr. S. I.
A. El Sheikh, Dr. B. C. Smith, and
Dr. M. E. Sobeir
Department of Chemistry
Birkbeck College (University of London)
Malet Street, London W.C. 1, (England)
111 M . E. Sobeir, B. C. Smith, A . N . Swamy, and M . Woods,
unpublished results.
Ionization Isomerism of Sulfinato Complexes of
Transition Metals
By Ekkehord Lindner and Giintev Vitzthun?1 * I
Sulfinato complexes are eminently suitable subjects for the
detection of various isomerism phenomena: alongside
stereoand valence isomers [21 we have now observed, for
the first time, ionization isomers.
Reaction of the potentially bidentate ligand ethylenediamine (en) with the sulfinato-O,O' complex ( p C H ~ C ~ H ~ S O ~ ) ~ M131
~ (inOethanol
H ~ ) Zat room temperature
affords the ionic compound [ P - C H ~ C ~ H ~ Sen21
O~M~
[p-CH3C6H4S02] ( I ) (yield about 70%). Compound ( I )
exhibits conductivity in ethanol and its cation could be
characterized in the form of [p-CH3C6H4S02Mn en2]
[B(CsH5)41 (2).
On repeated recrystallization from ethanol with tetrahydrofuran the metastable compound ( I ) is converted
irreversibly into the non-polar isomer ( J J - C H ~ C ~ H ~ S O ~ ) ~ M ~
en2 ( 3 ) , which is insoluble in all organic solvents. Composition and structure of the almost colorless sulfinato-O,O'
derivatives (1)-(3) were established by complete elemental
analysis and by the electronic and IR spectra, which indicate
a pseudo-octahedral environment of the Mn2+ ion (see
Table).
In every case, the coordinated p-CH3C6H4SO; ligand is
bonded to the central ion via both oxygen atoms ( 0 , O '
type) (41.
Table: SO2 stretching vibrations (in cm-I) of complexes ( 1 ) - ( 3 ) and
of p-CH,C&S02Na ( 4 ) .
In contrast, the isomer ( I c ) reacts with liquid SO2 to give an
orange precipitate of the complex [ ( O - C H ~ C ~ H &.PSO2]
(2), which is stabilized by specific attractions between omethyl groups and ligands. The phosphine oxide and phos970vs
IOOOvs, b
(3)
917s
1012vs
(4)
979 m
1027 m
(2)
~~
~~
The IR spectrum of ( I ) also contains the SO2 stretching
vibrations of the anion p-CH3C6H4SO; (cf. spectrum of
(4)), which are absent from that of (2). Thus ethylenediamine is bidentate in ( I ) and (2),but monodentate in ( 3 ) .
Possible stereoisomerism (cis-trans) in (3) cannot be detected
owing to the insufficient frequency splitting of va,(S02) and
Vs(SO2).
308
Angew. Chem. internat. Edit.
/ Val. 9
(1970)
1 No. 4
The product (2)is also a stable, colorless liquid (b.p. 158 "C]
749 torr); m.wt.: calc. 244.47, found 243, in benzene. IHN M R : singlet at 8 = --0.15 ppm (TMS as external standard);
IgF-NMR: singlet at 8 = -77.4ppm (CFC13 as external
standard).
RSOT
(3)
Received: February 6 , 1970
[Z 166 IE]
German version: Angew. Chem. 82, 322 (1970)
Priv.-Doz. Dr. E. Lindner and Dr. G. Vitzthum
Institut fur Anorganische Chemie der Universitiit
Erlangen-Numberg
852 Erlangen, Fahrstrasse 17 (Germany)
E. Lindrier and i:P. Loreriz, unpublished.
E . Lindner. G. Vifzthum. D . Larwner. and I . - P . Lore//-.
Angew. Chem. 82, 133 (1970); Angew. Chem. internat. Edit. 9,
160 (1970).
[3] E. Lincher and C. V i f z f h u r n , 2. anorg. allg. Chem.. in
press.
[4] E. Lindrter and G. Vifzfhttm, Chem. Ber. 102, 4053, 4062
(1 969).
Tris(N-trimethylsilylimido)sulfur and
Bis(N-trimethylsi1ylimido)sulfur Difluoride
Mass spectrum (relative intensities): molecular ion
SF2[NSi(CH3)& (8), Si(CH3); (loo), SFzNzSiz(CH3);
(72), SNZSi(CH3); (28), SiCH; (25), SN; (14), SN+ (14),
SFNSi(CH3); (7.9, N S F Z [ N S ~ ( C H ~ )(3),
~ ] - SFzNSi(CH3);
~
(3), SF[NSi(CH&I; (2), SFzNZSiz(CH3); (2).
IR (cm-1): 580 w, 620 s , 638 s, 700 w, 710 w, 735 w, 760 w,
787 w, 840 w, 889 w, 1258 s, 1302 s, 1430 vs, 2200 s , 3000 vs.
Raman (cm-1): 182, 195, 255, 338, 350, 582, 595, 620, 640,
698, 765, 790, 888, 1265, 1307, 1416, 1425.
Procedure :
NSF3 (30 g, 0.29 mole) is added dropwise to a stirred solution
of LiN[Si(CH3)3]2 (110 g, 0.66 mole) in light petroleum (b.p.
(150ml) at 0°C over a period of 1 h. After
40-60'C)
removal of solvent under reduced pressure, the products are
fractionated in a high vacuum; yield of ( I ) about l o g , of
( 2 ) , 15 g.
Received: February 16. 1970
[Z 167 IE]
German version: Angew. Chem. 82, 324 (1970)
. ..
~
-
[*I
Prof. Dr. 0. Glemser and Dipl.-Chem. J . Wegener
Anorganisch-Chemisches Institut d e r Universitgt
34 Gottingen, Hospitalstrasse 8-9 (Germany)
[ I ] Cf. R. Appel and B. Ross, Chem. Ber. 102, 1020 (1969);
Angew. Chem. 80, 561 (1968); Angew. Chem. internat. Edit.
7, 546 (1968).
By Osknr Gleinser and Jocrcliiiri Wegener[*]
We have now succeeded in synthesizing, for the first time, a
derivative of the hitherto unknown sulfur triimide, namely
tris(N-trimethylsilylimido)sulfur ( I ) , by reaction of sulfur
nitride trifluoride with lithium bis(trimethylsily1)amide in
light petroleum at O°C; the reaction also affords bis(N-trimethylsilylimido)sulfur difluoride (2). ( 1 ) is the only compound to have been discovered so far that contains 3-coordinate sulfur in the oxidation state + 6 and yet does not
polymerize "1.
Ethoxydiethylaminocarbenepentacarbonylchromium(0)
By Ernsf 0.Fisclter and Hans 1. KollmeierI+l
Alkyl- and aryllithium compounds react with transition
metal carbonyls t o give lithium acylcarbonylmetalates, which
can be converted into alkoxyalkyl- or alkoxyaryl complexes
by alkylation 121. We have now investigated whether lithium
amides can be made t o react in the same manner.
Reaction of lithium diethylamide and hexacarbonylchromium
in ether affords a colorless, crystalline product which we
regard as a 1 : 1 adduct and which, according to its IH-NMR
spectrum, is coordinated t o approximately one molecule of
ether.
Compound ( I ) is a stable colorless liquid (b.p. 204'C/748
torr), whose composition has been confirmed by elemental
analysis and cryoscopic molecular-weight determination (calc.
293.67; found 304) in benzene. The IH-NMR spectrum
contains only one signal at 8 = --0.15 ppm (TMS as external
standard).
Mass spectrum (relative intensities): molecufar ion
S[NSi(CH3)31; (3), Si(CH3); (loo), S[NSi(CH3)3]2NSi(CH,);
(25), S[NSi(CH3)&NSiHCH; (14), S[NSi(CH3)3]NSi(CH&
(6), NSNf (9,NS+ (5).
IR(cm-1): 72w, 175 w, 228s, 272s, 430w, 619s, 696s,
738 w, 758 w, 840 vs, 1260 vs, 1290 vs, 3000 vs.
Raman (cm-I): 97.5 dp, 130 pp, 175 dp, 212 dp, 230 dp,
257pp, 280p, 306dp, 533 p, 644p, 697p, 760p, 1005 p,
1127 p, 1262 p, 1290 p.
The I R spectrum (THF, LiF optics) of ( I ) contains four
V C ~ O
bands at 2034 m, 1939 w, 1897 vs, and 1870 s cm-J.
In the J H - N M R spectrum ([D,j]-acetone), the signals due t o
the OCzH5 protons appear at T = 6.6(q) and 8.9(t), and
S
at T = 7.45 (9) and 9.0 (t) in the
those of the N C ~ H protons
intensity ratio of approximately 1 : 1. The lithium salt ( I )
was ethylated with triethyloxonium tetrafluoroborate in
methylene chloride t o give ethoxydiethylaminocarbenepentacarbonylchromium(0) (2) as pale yellow crystals
(m.p. 29OC).
OLi
(CO)&r-C(
+
[(CZH~)@IBF,
N (C2H5)z
If the SN3 group is assumed to have a planar-trigonal structure (symmetry D3h), as is most probably the case, the double
bands at 1290 and 1260 cm-1 in the I R and at 1290 and 1262
cm-l in the Raman can be assigned t o a v3 mode, and the
strong, IR-inactive band at 1127 cm-1 t o a v1 mode.
Angew. Chem. internat. Edit. Vol. 9 (1970) / No. 4
309
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