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Cationic Thionitrosyl and Nitrosyl Complexes.

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[I811 D. M. Floyd, A. W. Fritz, C. M. Cimarusti, J. Org. Chem. 47 (1982)
176.
11821 M. J. Miller, P. G. Mattingly. J. Org. Chem. 46 (1981) 1557.
[I831 R. B. Sykes, J . Phillips, J Antimicroh. Chemother. 8 Suppl. E(1981).
[I841 a) S. Kishimoto, M. Sendai, S. Hashiguchi, M. Tommoto, Y. Satoh, T.
Matsuo, M. Kondo, M. Ochiai, J. Antihior. 36 (1983) 1421; M. Ochiai,
S. Kishimoto, M. Sendai, S. Hashiguchi, T. Matsuo, A. Imada, M. Kondo, Y. Kita in [44b], Abstr. No. 578: b) C. C. Wei, J. Tengi, M. Weigele
in [44b], Abstr. No. 324.
[IS51 J. A. Chan, E. A. Shultis, J . J. Dingerdissen, C. W. Debrosse, G. D. Roberts, K. M. Snader in [28bl, Abstr. No. 144.
11861 M. J. Miller, P. G. Mattingly, M. A. Morrison, 1. F. Kerwin, Jr., J. Am.
Chem. Sac. 102 ( 1980) 7026.
[I871 C. M. Cimarusti, R. B. Sykes, Med. Res. Reo. 4 (1984) 1; W. A. Slusarchyk, T. Dejneka, E. M. Gordon, E. R. Weaver, W. M. Koster, Heterocycles 27 (1984) 191; C. M. Cimarusti, D. P. Bonner, H. Breuer, H. W.
Chang, A. W. Fritz, D. M. Floyd, T. P. Kissick, W. H. Koster, D. Kro-
nenthal, F. Massa, R. H. Mueller, J. Pluscec, W. A. Slusarchyk, R. E.
Sykes, M. Taylor, E. R. Weaver, Tetrahedron 39 (1983) 2517.
[188] E. M. Gordon, M. A. Ondetti, J. Pluscec, C. M. Cimarusti. 0. P. Bonner, R. 8. Sykes, J. Am. Chem. Sac. 104 (1982) 6053.
[I891 S. R. Woulfe, M. J. Miller, Tetrahedron Lett. 25 (1984) 3293.
[190] A. Andrus, B. Partridge, J. V. Heck. B. G. Christensen, Tetrahedron
Lett. 25 (1984) 91 I.
11911 J. Blumbach, B. Mencke, B. C. Ross, K. H. Scheunemann, unpublished
results.
[I921 J. S. Skotnicki, T. J. Commons, R. W. Rees, J. L. Speth, J. Antihiof. 36
(1983) 1201.
[I931 G. Teutsch, A. Bonnet, Tetrahedron Leu. 25 (1984) 1561.
[I941 K. Yoshioka, T. Miyawaki, S. Kishimoto, T. Matsuo, M. Ochiai, J. Org.
Chem. 49 (1984) 1427.
11951 J. M. Clark, D. L. Weinberg, S. J. Olsen, D. P. Bonner, R. B. Sykes in
[28b], Abstr. No. 139.
[I961 Cf. S. Wolfe, A. L. Demain, S. E. Jensen, D. W. S. Westlake, Science
226 (1984) 1386.
COMMUNICATIONS
1
+ NO'AsF;
502. [CpFe(C0)2NO]"(AsF;)2
(2)
3
[Re(CO),S02]+AsF;
+ NS'AsF;
4
[Re(CO),NS]*'(AsF
;I2
(3)
5
4
Cationic Thionitrosyl and Nitrosyl Complexes**
By Gabriele Harimann and Riidiger Mews*
Compared to the seemingly countless number of nitrosyl
complexes that have been reported in the literature, the
number of hitherto unequivocally characterized organometallic thionitrosyl complexes is pathetically smal11',21.The
main reason for this is the lack of a general method of synthesis"l. Herein, it is shown that the thionitrosyl cationL4',
like the nitrosyl
could also provide a general entry to such complexes when used as reaction partner in the
form of the stable hexafluoroarsenate o r hexafluoroantimonate.
The complex cation of the salt 1IS1 reacts with N S + - and
NO +-salts with formation of the thionitrosyl- and nitrosylcomplex dications of the salts 2 and 3, respectively.
[CpFe(CO),S02]+AsF;
1
+ NS'AsF;
(1)
[CpFe(CO),NS]'+(AsF 6 j2
2
[*] Prof. Dr. R. Mews, Dr. G. Hartmann
[**I
202
Institut fur Anorganische Chemie der Universitat
Tammannstrasse 4, D-3400 Gottingen (FRG)
This work was supported by the Deutsche Forschungsgemeinschaft and
the Fonds der Chemischen Industrie.
0 VCH Ver~ag.~ge.~ellsclia~
mhH, 0-6940 Weinheim 1955
+ NO+AsF;
Ji-*
[Re(CO)sNO]2'(AsF~)z
(4)
In an analogous way, 4'61reacts with NS+AsF; to give
5 , but does not react with NO+AsF;.
The reactions (1)-(3) proceed quantitatively. At first
sight, the reaction of cations with cations to give dications
seems absurd; but, if one reflects on the bonding in SO,complexes such as 1 or 4['-'], such a reaction is perfectly
logical. The main contributer to formation of the metalsulfur bond is the n-back bonding from the metal to the ligand. Since SOr is only a weak n-acceptor, stronger nacids-such as, e.g., N S + or NO+-should replace this ligand. 4 does not react with NO+AsF; [Eq. (4)], thus indicating that the o-donor ability of the ligands (that of
NS+ is greater than that of NO') is of importance for
such reactions.
N O + can also replace CO in
[CpMn(CO),j + NO+AsF;
6
6
+ NS+AsF;
[CpMn(CO)2NO]+AsF;
7
[CpMn(CO),NS]+AsF;
8
(5)
(6)
In liquid SO2,the exchange proceeds according to Eq. ( 5 )
in high yields at room temperature, while 8 is formed almost quantitatively even at -60°C. However, since 8
readily eliminates CO i t was not possible to isolate the
compound in analytically pure form'"'. Due to a lack of
0570-0833/85/0303-0202 $ 02.50/0
Angew. Chem. Inr. Ed. Engl. 24 (7455)No. 3
sufficient data, no unequivocal statements could hitherto
be made about the ligand properties of NS+ compared to
those of NO+[']. It was concluded from a comparison of
the
IR
spectra
of
[CpCr(CO),N0]19.'21 and
[CpCr(CO),NS]1'31(see Table 1 ) that the NS+-ligand is the
better n-acceptor. The same conclusion was drawn from
the PE spectra and theoretical investigation^^'^^; yet it was
also shown that N S + is the better o - d ~ n o r ~ O
' ~n] changing
.
the d"-central atom M in the series of complexes
[CpM(C0)2NX]"+ (X = 0, S) from chromium(o) through
manganese(1) to iron(ir), the n-donor ability of the central
atom dramatically decreases; v(C0) and v(NX) shift to
higher wave numbers. The IR spectra of 2 and 3 show the
highest v ( N S ) and v ( N 0 ) frequencies thus far found for organometallic compounds. In the nitrosyl complex cations
of 3 and 7 the frequencies of the stretching vibrations lie
distinctly higher than in the corresponding thionitrosyl
complex cations 2 and 8, respectively, an indication of the
greater n-acidity of N O + .
Table I . Selected IR data of the complexes [CpM(CO)2NX]"+(AsF;),
(NuJol or Kel-F mull) [cm-'1.
[CpM(CO):NX]"
x=o
+
v(N0)
Chromium(n) 19, 12)
7
Manganese(1)
Iron(ii)
3
x=s
v(C0)
1706
2020/1946
1878 sh/ 2114/2075
1838 vs
1982
2198/2183
v(NS)
v(C0)
8
1165 202311963 1131
1284 (2108/2070)
2
1388
~
~
~
2178/2165
A comparison of the IR data (Table 1) confirms the hypothesis that the acceptor ability of NS' compared to that
of N O + depends on the charge density in the complex"51.
Experimental:
Exactly equimolar amounts ( 1 -2 mmol) of the transition-metal complexes
1, 4 or 6 , and of the N O + or N S + salts were weighed separately into a twolimbed flask in a dry box. After attachment of the flask to a vacuum apparatus, SO2 (15 mL) was condensed onto both substances simulataneously at
- 196°C and the resulting solutions combined at -60°C. After warming to
room temperature, the mixture was stirred for 12 h (in the case of 5: 3 d) and
the solvent removed. 2. 3, 5,and 7 remained in almost quantitative yield as
analytical pure residues"']. 8 is synthesized at -60°C and the solvent is removed in \acuo at -40°C'"'.
SO2 seems to be especially suitable for reactions with nitrosyl and thionitrosyl salts. whereas the solvents CH,CNI6l and CHICII1'" mentioned in the
literature can easily lead to exchange and decomposition reactions.
Received: March 21, 1984;
revised: January 15, 1985 [Z 767 IE]
German version: Angew. Chem. Y7(1985) 218
CAS Registry numbers:
1, 95217-85-9; 2, 95217-87-1; 3, 95217-89-3; 4, 95217-91-7; 5, 84303-53-7; 6,
12079-65-1 : 7, 95217-92-8; 8, 95217-94-0; [Re(C0)5NO]2+(AsF;)z, 95217-962; NS+AsFb, 31967-65-4; NO'AsF;, 18535-07-4; SOz, 7446-09-5.
[I] M. Herberhold, Nachr. Chem. Tech. Lab. 29 (1981) 365.
[2] H. W. Roesky, K. K. Pandey, Ado. Inorg. Chem. Radiochem. 24 (1983)
337.
[3] For example K. G. Caulton, Coord. Chem. Reu. 14 (1975) 317; N. G.
Connelly, Inorg. Chim. Acta Rec.. 6 (1972) 47.
[4] a) 0. Glemser, W. Koch, Angew. Chem. 83 (1971) 145; Angew. Chem.
Inr. Ed. Engl. I 0 (1971) 127; An. Asoc. Quim. Argent. 59 (1971) 127: b)
R. Mews, Angew. Chem. 88 (1976) 757; Angew. Chem. Inr. Ed. Engl. I5
(1976) 691
[ S ] G. Hartmann, R. Frobose, R. Mews, G. M. Sheldrick, Z. Naturforsch.
8 3 7 (1982) 1234.
161 R. Mews, Angew. Chem. 87 (1975) 669; Angew. Chem. I n [ . Ed. Engl. 14
(1975) 640; the salt 5 had already been prepared via an alternative
route: R. Mews, C . S. Liu, ibid. 95 (1983) 156 and 22 (1983) 158.
[7] B. E. R. Schilling, R. Hoffmann, D. C. Lichtenberger, J . Am. Chem. Soc.
101 (1979) 585.
Angew. Chem I n r . Ed Engl. 24 (198s) No. 3
[8] Cf. also P. R. Ryan, G. J. Kubas, D. C. Moody, P. J. Eller, Srrucr. Bonding (Berlin) 46 (1981) 47; C . Burschka, F. E. Baumann, W. A. Schenk, Z.
Anorg. Allg. Chem. 502 (1983) 191.
[9] E. 0. Fischer, H. Strametz, Z . Narurforsch. 8 2 3 (1968) 278.
[lo] N. G. Connelly, L. F. Dahl, Chem. Commun. 1970. 880; in 191 and [lo]
the synthesis of [ C P M ~ ( C O ) ~ N +PF;
O]
is described.
[I 11 Nitrosyl and thionitrosyl salts also react at low temperatures in liquid
SO2 with, e.g., the hexacarbonyls M(C0)6 (M =Cr, Mo, W) (R. Mews,
unpublished) to give products which have so far not been fully identified.
1121 E. 0. Fischer, 0. Beckert, W. Hafner, H. 0. Stahl, Z . Naturfor.sch. 8 1 0
(1955) 598.
1131 B. W. S. Kolthammer, P. Legzdins, J . Am. Chem. Soc. 100 (1978) 2247;
T. J. Greenhough, B. W. S. Kolthammer, P. Legzdins, J. Trotter, Inorg.
Chem. I8 (1979) 3548.
1141 J. L. Hubbard, D. L. Lichtenberger*Inorg. Chem. IY (1980) 1388.
[l5] M. Herberhold, P. D. Smith, H. G. Alt, J . Organomel. Chem. 191 (1980)
79.
[16] The elemental analyses of compounds 2, 3, 5 , and 7 are consistent with
the calculated values. 2 : wine-red solid, sparingly soluble in SO2, decamp. 172OC; IR (NuJoVKel-F mull): 3130 m, 2178/2165 vs, 2118 sh,
2080 m, 2020 m, 1429 s, 1420 s , 1388 vs, 1362 sh, 1338 sh, 1252/1250 w,
11 18 s , 1019 w, 1010 w, 880 s, 700 vs, 604 sh, 570 sh, 545 vs, 528 vs, 453
w, 438 w, 390 vs, 366 w, 320 w c m - ' . 3 : yellow-green solid, decomp.
137°C: IR (NujoVKel-F mull): 3128 s , 2198 vs, 2183 vs, 2140 sh, 2120
vw, 1982 vs, 1978 sh, 1963 sh, 1429 m, 1418 m, 1 I10 w, 884 m, 699 vs, 598
s, 568 s, 552 sh, 475 vw, 420 sh, 390 vs cm '. 5 : light-red solid, sparingly
soluble in SO,, decomp. 136°C; 1R (Nujol mull): 2220 vs, 2200 w, 2178
sh, 2160 vs, 2068 m, 2038 sh, 1370 vs, 700 vs, 542 m, 522 m, 488 w, 392 vs,
318 vw cm-'. 7: light'green solid, decomp. 136°C: IR (NujoVKel-F
mull): 21 14 vs, 2075 vs, 1878 sh, 1838 VS, 1430 w, 1420 w, I120 vw, 1022
vw. 869 m, 700 vs, 680 sh, 658 rn, 628 s, 530 w, 395 vs cm '.
1171 8 : light-brown solid; IR (NuJol/Kel-F mull): 3120 w, 2108 vs, 2070 vs,
1430 w, 1284 vs, 865 w, 700 vs, 672 w, 588 w, 568 w, 555 sh, 390 vs cm I.
The elemental analysis of 8 always shows C < 7 and an N : S ratio of
1 : 1 . On prolonged storage in solution at higher temperatures, 8 loses
CO quantitatively with formation of a solid which is insoluble in SO2.
Synthesis of
IE~ZN-C~W(C~)~(~-PP~~)~MO(CO)J',
the First Anionic Carbynemetal Complex;
Addition of COz to the W = C Bond**
By Ernst Otto Fixher*, Alexander C. Filippou,
Helmut G . Alt, and Ulf Thewalt
Dedicated to Professor Giinther Wilke on the occasion
of his 60th birfhday
We were able to demonstrate that neutral and cationic
carbyne(carbony1)metal complexes are obtainable on allowing carbene complexes to react with boron trihalides at
low temperature".']. In complete contrast, however, all attempts to isolate anionic carbyne complexes have hitherto
failed. Thus, for example, on reaction of stable, substituted
carbyne complexes of the type [Br(CO),L,WCR]
(L2 = phen, bpy ; R = C,H,, CHI) with KCN, replacement
of C O by CN' with formation of an anionic carbyne complex does not take place. Instead, as we have recently discovered, insertion of CO into the W=C bond takes place
with formation of an anionic ketene complex['I. This finding automatically raises the question whether this insertion
[*] Prof. Dr. E. 0. Fischer, DipLChem. A. C. Filippou
Anorganiscb-chemisches lnstitut der Technischen
Munchen
Lichtenbergstrasse 4, D-8046 Garching (FRG)
Priv.-Doz. Dr. H. G. Alt
Laboratorium fur Anorganische Chemie der Universitat
Universitatsstrasse 30, D-8580 Bayreuth (FRG)
Universitat
Prof. Dr. U. Thewalt
Sektion fur Rontgen- und Elektronenbeugung der Universitat
Oberer Eselsberg, D-7900 Ulm (FRG)
[**I Transition-metal carbyne complexes, Part 78. - Part 77: E. 0. Fischer. J.
Schneider, D. Neugebauer, Angew. Chem. 96 (1984) 814; Angenj. Chem.
Inf. Ed. Engl. 23 (1984) 820.
0 VCH Verlagsgesellschaft mbH. 0-4940 Weinheim 1985
0570-0833/85/0303-0203 $ 02.50/0
203
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