formation of iodobenzene from arenediazonium salts and i5-phosphorins (4)

1-Alkoxy-1-aryl-2,4,6-trisubstituted
iodide ions, with the h3- and h5-phosphorin respectively
B'
( 1 ) (1 mmol) is dissolved in a mixture of dry benzene
(15 ml) and the desired alcohol (10 ml). Reaction and work-
up of the likewise strongly colored I-alkoxy-1'-phos-
phorins (4)were as above.

Received: September 11, 1972 [Z 717b IE]

German version: Angew. Chem. 84,1146 (1972)
(3)

1 ArN20Uf4e
R'OH
(2)

Ar
[l] K . Dimroth, N . G r e s H.Perst, and F . W Szauber, Angew. Chem 79,
58 (1967); Angew. Chem. internat. Edit. 6, 85 (1967).
[2] K . Dimroth and W Sriide, Angew. Chem. 80, 966 (1968); Angew.
Chem. internat. Edit. 7, 881 (1968).
[3] K . Dimroth, A . Hettche, W. Stiide, and F . W. Steuber,Angew. Chem.
81, 784 (1969); Angew. Chem. internat. Edit. 8, 770 (1969).
Ar OR' [4] G. Miirkf, A . Merz, and H. Rausch, Tetrahedron Lett. 1971, 2989.
[5] If. Kanter, Diplomarbeit, Universitat Marburg 1972; H. Kanter
(4) and K. Dimroth, Angew. Chem. 84,1145 (1972); Angew. Chem. internat.
Edit. If, 1090 (1972).

Table 1. Compounds prepared (3a), p b ) , and (4a)-{4n}

OR' Ar RZ R4 R6 Yield M.p. ["C]

[%I [a1
43 130-132
41 221 -223
47 135-1 36
53 123-124
21 137-139
33 121-1 23
8 134-136
59 147- 149
24 171-172
64 149-151
23 203-205
4s 198-200
35 217-219
12 249-251
3.5 231-239
33 158-- I 60

[a] Analytically pure substance, yield not optimized

[b] Cyclohexyloxy.
[c] 2-Methyl-4-nitrophenyl.
[d] 2'-Methyl-4-nitro-4-biphenylyl.

in place of the readily polarizable and oxidizable iodide. Tetranitrosylchromium [Cr(NO)4]1"1

The composition of the new compounds was confirmed by
elemental analyses and spectroscopic data. I-Methoxy-
1,2,4,6-tetraphenyl-h5-phosphorin has already been pre-
pared by Mark1 et u Z . [ ~ ' from 2,4,6-triphenylpyrylium
tetrafluoroborate with phenylphosphane and methanol.
Compounds ( 3 4 and (3b) appear to be of special interest
since they number among the first I-fluoro-hs-phospho-
rinsf5].For instance, ( 3 4 gave the following NMR data
in C,D,: 'H-NMR (TMS internal standard): besides the
multiplet of aromatic protons a quartet at 6 = 8.01 ppm
(2H, 3,_,=33 Hz; 3,-,=6 Hz). "F-NMR (CFC1,
internal standard): S=25.6 ppm (sextet, .JF-,=1115 Hz;
.JF-H = 5.5 Hz); P-NMR (85%H,PO,external reference):
6=48.98 ppm (2m, Jf_,=1113 Hz).
I -Aryl-1 -jluor0-2,4,6-trisubstituted,
I5-phosphorins ( 3 )
Compound ( I ) (1 mmol) is dissolved in dry dimethoxy-
ethane (20 ml). (2) (1 mmol) is then added portionwise to
the stirred and cooled reaction mixture. The deeply colored
fluoro-h5-phosphorins (3) formed with evolution of N,
can be isolated by preparative layer chromatography with
benzenebight petroleum (1 : 1) on silica gel, and recrystal-
lized from methanol or ethanol.
By Max Herberhold and Abbas Razavi"'
Attempts to prepare the binary nitrosylmetal compound,
Cr(NO),, have so far failed"]. This mononuclear complex
is the last missing member in the isoelectronic series of
uncharged, tetracoordinated carbonyl-nitrosyl complexes,
the so-called pseudo-carbonylnickel series :
We have found that Cr(NO), is formed when a slow stream
of NO is drawn through an irradiated solution of Cr(CO),
in a hydrocarbon solvent (n-pentane, n-hexadecane, ben-
zene). The reaction can be followed by IR spectroscopic
measurement of the decrease in intensity of the C-0
stretching vibration of Cr(CO), (mode F,,, 1986 cm- in
n-pentane). According to the IR spectra, the unknown
[*I Doz. Dr. M. Herberhold and DipLChem. A. Razavi
Anorganisch-chemisches Laboratorium der
Technischen Universitat
8 Miinchen 2, Arcisstrasse 21 (Germany)
[**I These investigations were supported by the Deutsche For-
schungsgemeinschaft and the Fonds der Chemischen Industrie.

1092 Angew. Chem. inrernar. Edit. / Vol. I1 (1972) 1 N o . 12

compound Cr(CO),(NO),, which could conceivably occur
as an intermediate of the photoinduced nitrosylation, is not
formed in noticeable amounts ; furthermore, recarbonyl-
ation of the dissolved Cr(NO), by C O gas cannot be
achieved under the reaction conditions.
Cr(NO), dissolves in hydrocarbons to give intense reddish
brown solutions, which absorb over the whole range of the
visible spectrum. In n-hexane solution, absorption maxima
were recorded at x 750 nm (log E % 1.85), x 555 ( x 2.80),
458 (3.29), and ~290(3.61);a further maximum occurs
below 220 nm (log E > 4.7).
Formulation of the new complex as “Cr(NO),” is sup-
ported by the following facts :
1. Satisfactory elemental analyses (Cr, N) have been obtain-
ed, even though the air-sensitivity and high volatility of
the compound present considerable problems.-2. The
complex is diamagnetic (‘H-NMR).-3. The highest
peak in the mass spectrum corresponds to m/e=172, as
would be expected for Cr(N0): ; in addition, the mass
spectrum contains peaks for all the fragments expected to
occur by successive loss of NO ligands : Cr(N0,)’ (142),
Cr(N0): (112), Cr(NO)+ (82), Cr+ (52). All these frag-
ment ions show the characteristic isotopic pattern of
chromium.-4. The IR spectrum in the range 4000 to
’
800 cm- contains only one strong absorption (1721 cm-
in n-pentane), which can be assigned to the asymmetric
N r O stretching vibration (mode F,) in a tetrahedral
complex[21. Two additional bands appear at 650 and
’
496 cm- (in Nujol)13].
We assume, on the basis of these finding, that the reddish
brown complex of the composition Cr(NO), is isoelectronic
and isostructural with the colorless complex Ni(CO),.
A tetrahedral molecule of this type possesses only four
IR-active fundamentals, which belong to the triply degen-
erate representation F,[’]; three bands (~(NzEO),,,
v(Cr-NO),,, and G(Cr-N-O),,) appear in our IR spectra,
the fourth (S(ON-Cr-NO),,) should lie below 100 cm-’.
The two vibrations v(Cr-NO),, and G(Cr-N-O),, are
presumably strongly coupled, and the correbponding
bands at 650 and 496 cm- ought to be considered as ab-
sorptions of mixed character. The comparatively high
frequencies of these absorptions indicate a strong Cr+NO
back bonding; similar IR frequencies (646 and 556 cm- ‘)I4]
have been reported for the tetrahedral ion [Fe(C0),l2-
(cf. Ref. [ S ] ) , which is again isoelectronic with the pseudo-
carbonylnickel series.
0 German version : Angew. Chem. 84, 11 SO (1972)
N
It is tempting to extrapolate the valence force constants
k(N-0) of the carbonyl-nitrosyl complexes[‘’ Co(CO),NO
(14.6 mdyn/A), Fe(CO),(NO), (14.1), and Mn(CO)(NO),
(13.7) and to predict a k(N=O) value of ca. 13.2mdyn/A
for Cr(NO),. However, just how problematic such an
extrapolation can be is indicated by a comparison of the
valence force constants k(C-0) of the same compounds :
extrapolation of the k(C-0) values from the series
Mn(CO)(NO), (17.6 mdyn/A), Fe(CO),(NO), (17.1) and
Co(CO),NO (16.5) yields for the end member Ni(CO), a
value of ca. 15.9 mdyn/A2 which deviates considerably from
the value of 17.4 mdyn/A found experimentallyr6].
Angew. Chem. internat. Edit. Vol. 11 (1972) 1 No. 12
From purely formalistic considerations the central metal
in Cr(NO), can be assigned an oxidation state of -1V if-
as is usual-the nitrosyl ligand is considered as a NO’
cation. Actually, the effective charge on the chromium
should deviate very little from zero because of strong back-
bonding. In any case, Cr(NO), is an interesting counter-
part to the paramagnetic, tetracoordinated Cr+’“ com-
plexes (such as e.g. Cr[CH,C(CH,),],[’], Cr[l-norbor-
nyl],[’], Cr[CH,Si(CH,),],[9J, Cr(OR), (R = tert-
alkyl[lOslllor Si(C,H5)3[111),and Cr(NR,), (NR,=dial-
kylarnido)[”], to which a tetrahedral or pseudotetrahedral
structure has also been ascribed. It can be assumed that a
whole series of complexes of the general typeCr(NO).L,,-.,
exists (n=0-4; L=univalent, anionic ligand without
hydrogen atoms, e.g. neopentyl, tert-alkyl, trialkylsilyl-
methyl, tert-alkoxy or dialkylamido). Of this series, both
the end members (Cr(NO), and CrL,) and the mononitros-
ylchromium(1n) complexes Cr(NO)L, (L = e.g.
“ICH(CH3)2] 2 , “Si(CH3)312 OCH(CH312, OC(CH 313)
2
are already known[’31; according to an X-ray structure
analysis Cr(NO)[N(Si(CH,),),], has a pseudotetrahedral
structure with a linear CrNO group[’41.
The synthesis of transition metal-nitrosyl complexes by
photoinduced nitrosylation of carbonylmetal compounds
can be applied to other systems. Thus Mn,(CO),, is con-
verted stepwise into red Mn(CO),NO, green Mn(CO)(NO),,
and finally into a new nitrosylmangenese complex, which
is green and very volatile ( v ( N E 0 ) 1666 cm-’ in tetra-
hydrofuran). Similarly, the know complexes Fe(CO),(NO),
and (a-C,H,)V(CO)(NO),1’51 are formed when solutions
of Fe(CO), and (n-C,H,)V(CO),, respectively, are irra-
diated in solution and simultaneously treated with gaseous
N 0.
Experimental:
A stream of purified N O is passed through a solution of
Cr(CO), (220mg; 1 mmol) in n-pentane (300ml) which
is irradiated with a high-pressure mercury arc (Hanovia
L-450 W) until the strong IR absorption of Cr(CO), has
completely disappeared (ca. 2 hours). The intense reddish
brown solution is filtered in a nitrogen atmosphere and
evaporated at normal pressure to about 30 ml; the remain-
ing solvent is removed in a high vacuum at -78°C. The
extremely volatile complex, Cr(NO),, can be isolated as a
brownish black solid (m. p. 38-39°C in a nitrogen-filled
capillary) and purified by multiple sublimation at low
temperature: final yield ca. 50% (80-90 mg).
Received: October 3,1972 [Z 720IEl
-
[I] Cf : 8. F. G.Johnson and J . A . McClecerry, Progr. Inorg. Chem. 7,
277 (1966); W P. Griffiirh, Advan. Organometal. Chem. 7, 211 (1968).
[2] D. M . Adanis: Metal-Ligand and Related Vibrations. Edward
Arnold, London 1967, Chapt. 3, p. 84, 120.
[3] Raman investigations are rendered difficult because of the intense
color of the complex.
[4] W F . Edgell, J . H U E J . Thomas, H . Lehman, C. Angel/,and G . Asaro,
J. Amer. Chem. SOC.82,1254 (1960).
[5] H . Stammreich, K . Kawai, E: TacarPs, P . Krumholz, J . Behmoiras,
and S. Brit, J. Chem. Phys. 32, 1482 (1960).
[6] C. G . Barraclough and J . Lewis, J. Chem. SOC. 1960,4842.
[7] W Mowat and G. Wilkinson, J. Organometal. Chem. 38, C35
(1972).
[8] B. K . Bower and H . G. Tennent, J. Amer. Chem. SOC.94, 2512
(1972).
[9] G . Yagupsky, W Mowat, A. Shortland. and G . Wilkinson, Chem.
Commun. 1970,1369; W Mowat, A. Shortland, G. Yagupsky, N . J . Hill,
M . Yagupsky, and G. Wilkinson, J. C. S. Dalton 1972, 533.
1093
[lo] N . Hagihara and H . Yamazaki, J. Amer. Chem. SOC.81, 3160
(1959); H. Yamazaki and N . Hngihara, Nippon Kagaku Zasshi 81,
821 (1960); Chem. Abstr. 56, 1589 (1962).
[ll] E . C. Alyea, J . S. Basi, D.C. Bradley, and M . H . Chisholm, J. Chem.
SOC.A 1971, 772.
[I21 J . S. Basi and D. C . Bradley, Proc. Chem. SOC. (London) 1963.
305; J . S . Basi, D. C . Bradley, and M . H . Chisholm, J. Chem. SOC.
A 1971, 1433.
[13J D.C. Bradley and C . W. Newing, Chem. Commun. 1970,219.
[I41 D. C. Bradley, M . B. Hursthouse, C. W Newing, and A. J . Welch,
J. C. S . Chem. Commun. 1972, 567.
[15] E. 0.Fischer, R . J J . Schneider, and J . Miiller, J. Organometal.
Chem. 14, P4(1968); E. 0. Fischer and R. J . J . Schneider, Chem. Ber. 103,
3684 (1970).
Reaction of CIF, with OF2:Preparation and
Properties of Chlorine Oxide Trifluoride and the
Existence of Chlorine Oxide Pentafluoride"]
By Klaus Ziichner and Oskar Glemser[*I
Irradiation of a gaseous mixture of ClF, and OF, in
a quartz flask leads to formation of white crystalline
[ClOF,]: [SiF6I2-, which melts under its own vapor
pressure at 50.5"C and dissociates into ClOF, and SiF,,
both of which can be detected in the gaseous phase by
IR and mass spectrometry. Subsequent cooling leads to
reformation of [ClOF,]; [SiF,]'-, which is also formed
from ClOF, and SiF, at room temperature.
Chlorine oxide trifluoride CIOF, ( I ) , which was recently
prepared via another route[21[**],was characterized by
elemental analysis, mass, IR, Raman, and I9F-NMR
( 2 . 6 ) , 3 5 ~ 1 ~(7.8);
+ 3 7 ~ 1 0 +(II.I), 3 5 ~ 1 (32.8);
0 ~ ~37c1+
(0.6), 37Cl+ (2.8), H3,C1+ (2.4), ,'Cl+ (8.9); HF' (2.Q
F + (2.2); O + (1.5).-I9F-NMR (CFCl, as external
standard): &,,-253 ppm. The vibration spectra are
given in Table 1 along with a tentative assignment of the
bands assuming C, symmetry for the molecule. We are of
the opinion that our assignment of the bands is more
probable than that by Bougon et ai. assuming C,, sym-
metry.
We have studied the reactions of ( I ) both with Lewis
acids and with Lewis bases. Reaction with AsF,, SbF,,
and SiF, affords the white salts [C10F2]+ [AsF6] -,
[CIOF,]' [Sb,F, ,]-, and [ClOF,]; [SiF,]'-, the first
two ofwhich can also be prepared from [C10F,]i[SiF6]Z-
by reaction with AsF, and SbF, respectively at room
temperature with removal of SiF,. The Raman spectra
of the salts containing the [ClOF,]+ ion are in complete
agreement with those given in the literature[31. The
hexafluoroarsenate and the new hexafluorosilicate may be
quoted asexamples. Raman spectrum [cm- '1 of [ClOF,] +:
[ClOF,]' [AsF6]- (values in brackets: cf. Ref. [3]):
v1 1335 (1332), v1 1325 (1321); v, 763 (760); v3 513
(511); v4 410 (408); v, 747 (725); v6 not observed.
[C1OF,]i[SiF6I2-: v1 1333, v1 1324; v, 728; v3 521;
vq 428 ;v, not observed ;v6 383.
Reaction of ( I ) with fluoride ion as Lewis base leads to
formation of the hitherto unknown oxotetrafluorochlorate
ion [C10F4]- :
ClOF, + CsF -20 "C
C S +[CIOF,]'

spectra'"]. Mass spectrum (rel. intensity in %): 37C10Ff The bands in the Raman spectrum [cm- '1 of the [ClOF,] -
(30), 3 5 ~ 1 0 ~(100);
; 3 7 ~ 1 ~(0.8),35~1~:
; (2.8); 37c10~+ ion were assigned, by analogy with the assignment of the
(25.6), 3 5 ~ 1 0 (78.9);
~ + 3 7 ~ 1 0 : (IA), 3 5 ~ 1 0 : (2.2); 3'c1~+ bands in the Raman spectrum of XeOF4[41,as follows:

Table 1. Vibration spectra of CIOF, (1)

-~ ~

Raman (liquid) [cm-'1 IR (gaseous) [cm-'1 Assignment

1370 W
1233 m P 1226 S
1216 m
1165 W
1155 W
980 W
900 W
730 Sh, w
695 S P 697 Sh, m
- (684) [a1
668 Sh, m dp? 6 76 VS
498 Sh, w P 500 m
46 7 VS P 478 m
406 w p'! 400 W

320 W dP 325 m
230 m dP 230 W

[a] Determined from combination vibration

v1 1202(w); v2 455 (vs); v3 410 (s); v4 349 (vs); v, - ;v6 285

[*] Prof. Dr. 0. Glemser and Dip].-Phys. K. Ziichner
Anorganisch-chemisches Institut der Universitat
34 Gottingen. Hospitalstrasse 8-9 (Germany)
[**I Note added in proof (26. Oct. 72): In the meantime a series of
reports on CIOF, have been published : D. Pilipooich, C . B. Lindahl,
C . J . Schark, R. D. Wilson, and K . 0. Christe, Inorg. Chem. 11, 2189
(1972); D. Pilipouich, H. 61. Rogers, and R. D. Wilson, ibid. 11, 2192
(1972); K . 0. Christe and E. C . Curtis, ibid 11,2196 (1972); C . J . Schack,
C . B. Lindahl, D. Pilipouich, and K . 0. Christe, ibid. 1 1 , 2201 (1972);
K . 0. Christe, C . 3. Schack, and D. Pilipouich, ibid. 11, 2205 (1972);
K . 0.Christe and E. C . Curtis. ibid. 11, 2209 (1972); K . 0. Christe.
E . C. Curtis,and C. J . Schack, ibid. 1 I , 2212 (1972).
(m); v7 - ; v8 - ; vg 204 (w).
If the photochemical reaction of ClF, and OF, is carried
out in a nickel vessel fitted with sapphire window the
principal product is ClOF, ( I ) ; small amounts of CIOF,
(2) are also formed, but this could not be isolated in pure
form. The mass spectrum (negative ions!) of the reaction
product contains the fragments 37C10F4, 35C10F,,
37C10F;, and 35C10F;, which can originate only from
( 2 ) , since the spectrum of pure (1) does not contain

1094 Angew. Chem. internat. Edit. 1 Vol. I1 (1972) / N o . I.?