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Metal-Ligand Bonding in Sulfinato Complexes of Transition Metals.

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cinic anhydride and with tetracyanoethylene to yield I-tricyanovinylazulene "1.
In contrast, the 5-azaazulene system [21 is able to enter into
cycloadditions with alkynes, the heterocycle undergoing
simple conversion into previously inaccessible derivatives of
carbocyclic azulene. 6-Phenyl-5-azaazulene ( I ) 131 reacts
with an excess of tolan a t 350 O C to give 30 % of 5,6-diphenylazulene (3a) [41 and benzonitrile, as well as 5 % of 4,5,6-triphenylazulene (5a) and hydrocyanic acid. Formation of (3a)
and ( 5 a ) would suggest the intermediacy of the 1,4 adducts
( 2 a ) and (4a) and their Alder-Rickert cleavage to the carbocyclic azulene. Disrotatory thermal valence isomerization of
( I ) t o (7) and (81, which is forbidden by the WoodwardHoffmann rules [Sl, and subsequent elimination of benzonitrile or hydrocyanic acid t o give the pentalenes (9) and
( l o ) , respectively, which could also react with tolan to give
(3a) and (5a) [61, was ruled out by experimental findings 131:
to carbocyclic azulene derivatives and pyridine profits from
the energy gain involved in formation of the cyclic conjugated systems.
Received: November 29, 1969
[Z 128 I€]
German version: Angew. Chem. 81,135 (1970)
[*I Prof. Dr. K. Hafner, J. Hhring, and Dr. W. Jake1
lnstitut fur Organische Chemie der Technischen Hochschule
61 Darmstadt, Schlossgartenstrasse 2 (Germany)
[11 W. Treibs, Naturwissenschaften 47, 156 (1960); K . Hafner
and K . L . Moritz, Liebigs Ann. Chem. 650, 92 (1961). According
to V. Orfanos (Dissertation, Technische Hochschule Darmstadt
1968), dimethyl 4,8-bis(dimethylamino)azulene-5,6-dicarboxylate
combines with dimethyl acetylenedicarboxylate to give an orangered 1:l adduct o f m.p. 126-128 "C, whose structure has not yet
been fully elucidated. Aceheptylenes (cyclohept[cd]azulenes) are
able to undergo Diels-Alder reactions with maleic anhydride and
tetracyanoethylene: K . Hafner and J . Schneider, Liebigs Ann.
Chem. 624, 37 (1959); K. Hafner and G . Schneider, ibid. 672, 194
[2] K . Hafner and M . Kreuder, Angew. Chem. 73, 657 (1961);
K. Hafner, K . H . Hafner, C . Konig, M . Kreuder, G . Ploss, G .
Schulz, E. Sturm, and K . H . Vdpel, ibid. 75, 35 (1963); Angew.
Chem. internat. Edit. 2, 123 (1963).
[3] W. Jiikel, Dissertation, Technische Hochschule Darmstadt
1968. Results obtained so far from mass-spectrometric studies on
gas-phase pyrolysis of ( I ) do not rule out its decomposition to
( 9 ) and benzonitrile.
141 Correct analyses were obtained for all compounds described.
[5] R. B. Woodward and R. Hoffmann, Angew. Chem. 81, 797
(1969); Angew. Chem. internat. Edit. 8, 781 (1969).
[6] E. Le Coff, J. Amer. chem. SOC.84, 3975 (1962).
[71 G. Wirrig and H . L . Dorsch, Liebigs Ann. Chem. 711, 46
[8] U . Miiller- Westerhoff and K . Huffier, Tetrahedron Letters
1967, 4341; H . J . Lindner, Chem. Ber. 102, 2464 (1969).
[9] J . Sauer, Angew. Chem. 79, 76 (1967); Angew. Chem. internat. Edit. 6 , 16 (1967).
Metal-Ligand Bonding in Sulfinato Complexes of
Transition Metals
By E. Lindner, G . Vitzthum, D . Langner, and I.-P. Lorenz[*l
Bis- and tris(su1finato) complexes are formed in the reaction
of sodium sulfinates with soluble compounds of divalent and
trivalent transitions metals in water or alcohol:
n RS02Na
+ MXn
l-Methyl-6-phenyl-5-azaazulene and 4-methyl-6-phenyl-5azaazulene give different azulenes with tolan. If the reaction
sequence ( I ) +(7) +(9) were to apply, then both azaazulenes
would give I-methylpentalene and thus either the same methyldiphenylazulene or an identical mixture of isomers.
Evidence for 1,4-adduct formation during reaction of ( 1 )
with acetylenes comes from the reaction of ( 1 ) with cyclooctyne[71 in the molar ratio 1 : 4 at 170°C (reaction time:
15 s). From the reaction mixture a 25 % yield of the 1,4
adduct (26) can be isolated, whose Alder-Rickert cleavage
(250 ' C ; 30 s) affords 5,6,7,8,9,10-hexahydrocycloocta[f]azulene (36) (60 %)and a minor amount of 3-phenyl-5,6,7,8,9,l0-hexahydrocycloocta[c]pyridine (66). The strained adduct
(46) was also expected but, unlike (2b), decomposes to 6-
(30%) under the reaction conditions.
The hetero atom in the seven-membered ring of the 5-azaazulene system alters the electron distribution and reduces the
Ji-electron delocalization compared with the azulene system [81. This effect is probably responsible for the 1,4 addition
of the cc,p-unsaturated azomethine partial structure in ( I ) t o
the alkynes. The reaction may proceed viu a Diels-Alder
reaction "with inverse electron demands"r91 or as a two-step
cycloaddition. Decomposition of the 1,4 adducts ( 2 ) and ( 4 )
+ M(SOZR)~ n NaX
(n =
2 ) Zn
3 ) Cr
halogen, acetate)
The toluene- and benzenesulfinato complexes of zinc, cadmium "], and mercury [21 (la)--(36) have already been described. We have now succeeded in preparing bis(methanesu1finato)mercury (3c) and -zinc ( l c ) as the S-type.
Apart from the anhydrous mercury compounds (3a) and
(36) [31, little has been known about the structure of the complexes (Ia)-(2b) except that the RS02- ligands are linked t o
M2+ via oxygen.
We have now found that the type of bonding of the ligands
to the metal ion in (Ia)-(3b) is particularly dependent on the
wafer content of the compounds.
The benzene- and methanesulfinato complexes (161, (261,
(36), and (3c) prepared in water at room temperature are
Angew. Chem. internat. Edit. / Vol. 9 (1970) 1 No. 2
obtained as dehydrated salts after drying over P40i0 in a
vacuum at 25 “C for 12 h. Under the same conditions, the p toluenesulfinato complexes (/a)-(3a) crystallize as 1 : 2
adducts with water; the “crystal water” can be removed
from (lo)--(3a) by drying for a period of 60 h, in the case of
( l a ) at temperatures above 120°C and in the case of (2a)
and (3a) -contrary to previous reports [ I ] --- at a temperature
as low as 25 ‘ C .
If KBr pellets are prepared in a moist atmosphere, the IR
spectra of (16)-(36) are surprisingly similar to those of ( l a )
to ( 3 a ) ; all the compounds (except ( 3 c ) ) then contain water
and in accordance with the slight difference in frequency between vs(S02) and vas(S02) (cf. Table 1) are to be formulated as distorted octahedrally configurated bis(su1finato-0,O’)
diaqua complexes. Inter- o r intramolecular arrangement of
the RS02- groups cannot be differentiated.
The large frequency difference and the shortwave position of
vs(S02) and vas(SOz) indicate that the anhydrous mercury
complexes (3a)-(3c) are S-bonded.
During the conversion of hydrated into the anhydrous cadmium compounds (2n) and (26) a reversible re-orientation
of the bonding of the RSO; ligands to the Cd2+ takes place;
the IR spectra of the anhydrous complexes points to a
sulfinato-0 bonding (large frequency difference, longwave
v,,(SOM) bands 131).
Table 1 .
Three SO bands having the irreducible representation A2 +
2 E are found in all cases. Accordingly we assume the complexes (4a)-(5c) to have an octahedral configuration with
D3 symmetry as is also indicated by the electronic spectrum.
The RSO2- ligands are linked via both oxygen atoms to the
central ions (small frequency difference: sulfinato-0,O’
type). The solubilities - ( 4 c ) and (Sc) are very readily soluble in ethanol -- also indicate that these compounds are
Received: October 24, 1969; revised: December 6, 1969 [ Z 129 IE]
German version: Angew. Chem. 82, 133 (1970)
[*] Priv.-Doz. Dr. E. Lindner, Dr. G. Vitzthum,
Dipl.-Chem. D. Langner, and I.-P. Lorenz
Institut fur Anorganische Chemie der UniversitHt
852 Erlangen, Fdhrstrasse 17 (Germany)
[l] G. B. Deacon and P . G. Cookson, Inorg. nuclear chem.
Letters 5 , 607 (1969).
[2] G. B. Deacon, Austral. J. Chem. 20, 1367 (1967).
[3] E. Lindner and G. Vitzthum, Chem. Ber. 102, 4053, 4062
(1969); E. Lindner, G. Vitzthum, and H. Weber, Z . anorg. allg.
Chem., in press.
[4] N. A . D . Carey and H. C. Clark, Canad. J. Chem. 46,649
SO2 stretching vibrations (cm-1) of sulfinato complexes of zinc, cadmium, and mercury.
1 (a)
with H2O
1 (b)
943 vs
989 vs;
1 Assignment
1 (c1
Bond type
Sulfinato-0 0’
958 sh
942 vs
without HzO
without HzO
1050 rn, I020 sh
971 vs, 963 vs
1051 m, 1024 w
1003 rn, 985vs
962 vs
1031 s;
1030 s;
924 m
1025 sh, rn;
9 3 0 s 141
960 s
919 m
with HzO
947 vs
with H 2 0
1037 vs;
980 s
9 8 8 ~ ; 965sh
946 vs
1229 m; 1040 vs
1203 vs
1194 vs; 1037 vs
1177 vs.
Interpretation of the spectra of anhydrous ( l a ) and ( I b ) is
difficult since in addition to the bands of medium intensity
(indicative of sulfinato-0 complex) very intense absorptions
also occur, which, o n account of their position and frequencydifference, are characteristic of a sulfinato-0,O’ complex:
very probably the 0,O‘ type bond preponderates in this
particular case. In contrast to Carey and Clark141 we have
found that (CH3S02)2Zn formed by a n “SO2 insertion” reaction, like ( l a ) and ( I b ) , is a sulfinato-0,O’ complex (cf.
Table 1). We were able to prepare for the first time the sulfinato-S isomer [H3C(Oz)S]2Zn (vas(S02) = 1190 vs,
vs(S02) = 1060 cm-1 s) according to eq. (1).
The green and the yellow tris(p-toluene-, benzene-, and
methanesulfinato) derivatives, respectively, of chromium
(4a)-(4c) and of iron ( S a ) - - ( 5 c ) are characterized by intense SO stretching vibrations i n the region 90&1000 cm-1
(cf. Table 2).
Table 2. SO stretching vibrations (cm-’) of tris(su1finato)
complexes of chromium and iron.
i 51
972 sh (A,)
940 vs (E)
927 vs (E)
967 sh ( A Z )
945 vs (E)
925 vs (E)
964 sh (A,)
947 vs (E)
925 vs (E)
(A,) masked
952 vs (E)
942 vs (E)
(A,) masked
948 vs (E)
938 vs (E)
967 S, sh (A2)
946 vs (E)
919 vs (E)
Angew. Cheni. internat. Edit.
i Vol. 9 (19701 J No. 2
1061 vs
Unusual Cleavage of Sn,Sn-Disubstituted
Oxastannadihydroanthracene by Electron Impact
By I . Lengyel and M. J . Aaronson [*I
The two most abundant ions in the mass spectra of 10,lO-dialkyl-9-oxo-l0-stanna-9,lO-dihydroanthracenes( I ) (R =
nC,H2m+l, m > 2 ) are (2) and (31, resulting from initial
Sn-Calkyl bond cleavage followed by elimination of a neutral
alkene from the second 10-alkyl group with concomitant shift
of a hydrogen atom to the metal in (3) [e.g. in compounds
( l a ) and ( I b ) ] .
In this connection, it was of eminent interest to investigate
related compounds constructed in such a way that no easilytransferable hydrogen is available from the substituents in
position ten. Suitable models to meet this condition appeared
to be the derivatives ( 1 c ) - ( l e ) [2J. Their mass spectrai31 still
exhibit predominant peaks for the ions (2c)-(2e) but no
peaks for (3c)-(3e).
Subsequent fragmentation takes a different course, involving
competitive expulsion of different neutral particles. The most
favored path of further decomposition is ejection of the elements of dibenzofuran, to give ions (4c)-(4e), confirmed by
the presence of the appropriate metastable peaks for compounds ( I d ) and ( l e ) . Alternatively, elimination of particle
C6H4O leads to ions (Sc)-(5d). Finally, for ( I d ) , there is the
interesting loss of C6H4 (dehydrobenzene), again confirmed
by a metastable peak at m,/e 228.8 (this value applies to the
12oSn isotope 149, to give ( 6 ) ,m / e 289.Theelimination of C6H4
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bonding, metali, sulfinato, transitional, complexes, ligand
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