ZTL PL: Parameter (N I (H 2 0) N) 2+

Notes 295
(D) Effect of azide ion on energy level splittings of nickel( l i ) ion

The energy of the lowest transition for Ni(II) ion in an octahedral field (3A2o--->aTzu) is equal to A
(10 Do). The energy difference between the 3p and 3F states is dependent on covalence in bonding. The
lowering of the ap state is a measure of covalence, in addition to some other factors, and may be ex-
pressed by off. An attempt is made to see the effect of azide ion, as a ligand, on the energy level splitt-
ings of Ni(ll) ion[28]. Figure 4 shows the absorption spectra of nickel perchlorate (0.04 M) and of a
nickel azide solution with [Ni2+]:[N3 -] of 1:32. The concentration of Ni 2+ in this mixtures is also
(0.04 M). Band maxima and band intensities of Ni(ll) ion were affected on mixing with Na-. Positions
of band maxima, in a complex ion, is dependent on the basicity of the ligand whereas the intensity of an
electronic transition is a measure of how far it is allowed or forbidden. In [Ni(H20)sNa] +, distortion
Table 2. Comparison between some physical para-

meters of the ions: [Ni(H20)6] 2+ and INi(HzO)sNa] +
Parameter [Ni(H20)n] 2+ [Ni(H20)sN3] +
ZA2~-"* aTz. 8547 cm -1 8696 cm -I

3A2~ -o 3TI,~r~ 14,286 cm -1 14,226 cm -1
3A2~ ---> ZTl~pl 25,641 cm -1 24,390 cm -1
Dq 855 cm -1 870 cm -t
E:ZT1g~p~ 15,381 cm -1 13,950 cm -t
X 14,241 cm -1 13,708 cm -1
o/3 10.1% 13.5%
from the simple cubic symmetry may exist. Hence, symmetry forbidden transitions will be more
allowed and of higher intensity. From Fig. 4, the numerical values of some physical parameters of
hexaaquonickel(II) and monoazidopentaaquonickel(II) complexes were calculated (Table 2). Results
given in Table 2 indicate that bond covalency is greater in the azido than in the aquo complex ion.
Chemistry Department R. A B U - E I T T A H
Faculty of Science S. E L M A K A B A T Y
Cairo University
G iza, Egypt
28. Y. Tanabe and S. Sugano, J. phys. Soc., Japan 9, 753 (1954).
J. inorg, nucl. Chem., 1973, Vol. 35, pp. 295-297. Pergamon Press. Printed in Great Britain
The reactivity of cobaltocene as compared to ferrocene
(First received22 November 1971 ; in revised form 12 Apri11972)
IT HAS BEEN tentatively deduced that[l, 2] ferrocene (CP)zFe (CP = cyclopentadiene) and a number
of proton acids, H B, form charge transfer complexes of the type [(CP+)2Fe][H-B]. This structural de-
duction was based on magnetic moment, ESR, kinetic and chemical evidence[l, 2]. The interest in
metallocenes as electron donor is due to the fact that the electron transfer process is accompanied by
1. M. M. Aly, R. Bramely, J. Upadhyay, A. Wassermann and P. Woolliams, Chem. Comm. 404

(1965).
2. M. M. Aly, D. V. Banthorpe, R. Bramely, R. E. Cooper, D. W. Jopling, J. Upadhyay, A. Wasser-
mann and P. Woolliams, Monatsch. Chem. 98, 887 (1967).
296 Notes
the formation of their cations which differ in stability. This difference in stability and its relation to the
electronic structure of the different metallocenes led us to the investigation of a system in which
cobaltocene is the electron donor and proton acids causing its oxidation in organic solvents.
On mixing 40 ml of a de-aerated benzene solution of cobaltocene (0.0244 moles) with an equal
volume of de-aerated benzene solution of trichloroacetic acid (0.244 moles) a greenish yellow pre-
cipitate was formed. The latter was filtered off and recrystallized from benzene-methylene dichloride
I : 1 mixture to yellow needles, m.p. 133°C. Yield 6.1 g (37 per cent of the theoretical yield). Found, %,
C, 28.57; H, 2.00; CI, 47.25; Co, 8.86. C16H12C19CoO6 requires %, C, 28.34, H, 1.78; C1, 47.02; Co, 8.69.
The filtrate from the crude product was extracted with 100 ml water and the chloride ion content of
the aqueous extract showed that 0.91 mole of chloride ion was formed for every 1.0 mole of cobalticen-
ium salt isolated. This salt was found to be diamagnetic in nitromethane solution using the N M R
method [3]. The i.r. spectrum of the salt in nujol mull is a composite of its components spectra (695 s,
705 w, 835 s, 840 w, 870 m, 900 m, 1008 s, 1105 w, 1250 s, 1418 s, 1740 s, 2100 w, 2550 w, 2700 w,
3095 s, cm-1). Two moles of either sodium hydroxide (in water) or piperidene (in methylene dichloride)
were consumed for every mole of the salt in the potentiometric titration. The electronic spectrum of the
salt in water exhibits two peaks at 405 nm (~ 2.35 × l02 I. mole -~ cm -1) and at 265 nm (E 3.38 x l04 I.
mole -1 cm-~). The molar electrical conductivity of the salt in nitromethane, 10-aM solution, is 73 ~-~
mole -~ cm 2 indicating a 1 : 1 electrolyte]4]. These results are compatible with regarding the isolated
salt as the cobalticinium trichloroacetate with 2 moles of trichloroacetic acid as molecules of crystal-
lization.
A similar reaction with picric acid produced a dark brown precipitate which was filtered off, and
extracted with I00 ml boiling methylene dichloride. On cooling the solvent brownish yellow needles
were precipitated, m.p. 265°C with detonation. Found %, C, 45.87; H, 3.17; N, 10.52; Co, 14.37;
C~6H~2NaCoO7 requires %, C, 45.96; H, 3-14; N, 10.05; Co, 14.10. This salt was found to be dia-
magnetic in nitromethane using the N M R method]3]. The i.r. spectrum was a composite of its com-
ponents spectra, and its electronic spectrum in water was identical with that described for the
cobalticenium picrate [5] (three peaks at 410-405, 310-305 and at 265 nm). The molar electrical
conductance of the salt in nitromethane, 10-3M solution, is 63 fl -~ mole -1 cm 2 corresponding to a 1:1
electrolyte [4]. These results are compatible with identifying the isolated salt as the cobalticenium
picrate.
Reaction of ferrocene with picric acid in benzene, under similar conditions to that described above,
produced an immediate colour change from yellow to brown. The reaction mixture was saturated with
oxygen, which is known to have a catalytic effect]l], and left for 30 days. No precipitate was formed,
and the colour did not change during this interval. 100 ml n-pentane were added to the reaction mixture
in order to precipitate the formed ferricenium picrate [6]. The latter was filtered off and purified from
picric acid impurity by extraction with benzene. The purified material was only sufficient for m.p., and
mixed m.p. 172°C with detonation, and for recording the electronic spectrum (two peaks at 620 and
250 nm). 95 per cent of the added ferrocene was recovered unchanged.
It appears that the radical anion ]H-B] which was suggested to be formed when the donor was
ferrocene ] I, 2] could not be isolated when the electron was donated from cobaltocene. If this radical
was formed in this case then it would be expected that the isolated product from the reaction with
trichloroacetic acid to have a paramagnetic moment of 1.73 B.M. The formation of chloride ions in
this reaction could be explained by the reaction of the electron, removed from cobaltocene, with the
chlorine atoms of the acids. A similar observation was reported [7] for the reaction of hydrated elec-
trons with chloroacetic acid. It could be suggested that the activated complex formed in the case of
cobaltocene is structurally different from the bridged activated complex reported for the case offerro-
cene[1]. This assumption is supported by the observation that the reaction of cobaltocene with
trichloroacetic acid is almost an instantaneous reaction which takes place in the absence of oxygen,
while the same reaction with ferrocene was not a fast reaction and was found to be catalyzed with
3. D. F. Evans, Proc. chem. Soc. 115 (1958); J. chem. Soc. 2003 (1959).
4. J. F. Coetzee and G. P. Cunningham, J. Am. chem. Soc. 87, 2529 (1965).
5. G. Wilkinson, J. Am. chem. Soc. 74, 6148 (1952).
6. (3. Wilkinson, M. Rosenblum, M. C. Whiting and R. B. Woodward, J. Am. chem. Soc. 74, 2125
(1952); J. Jack and N. Sutin, J. inorg, nucl. Chem. 7, 5 (1958).
7. E. Hayon and A. O. Allen, J. phys. Chem. 65, 2181 (1961).
Notes 297
oxygen [ 1]. This difference between the chemistry of cobaltocene and that of ferrocene is extended to
their respective cations. The ferricenium cation was found to be quantitatively reduced to ferrocene by
the action of the hydroxyl ion[l, 2]. The cobalticinium cation, on the other hand, did not seem to be-
have similarly, and the two moles of hydroxyl ion or piperidene consumed for every mole of the tri-
chloroacetate salt are accounted for by the presence of 2 moles of trichloroacetic acid associated with
every mole of the salt. This observation is in agreement with that reported by Wilkinson [8] who found
that the action of strong reducing agent, like Li-A1 hydride, on the cobalticenium cation leads only to a
partial hydrogenation of the cyclopentadiene ring.
Apart from the differences in the approaches discussing the electronic structure of metallocenes
there are, to a large extent, a common agreement about ascribing the metal-cyclopentadiene bonding
to the E ~ orbitals, and about assigning the unpaired electron in cobaitocene to the antibonding
E*2g levels[9]. This assignment is compatible with the observed reactivity of cobaltocene towards
trichloroacetic acid and picric acid, and with the stability of the formed cation which is isoelectronic
with ferrocene.
Protonation of the metal atom in ferrocene was suggested to account for the observed high field
absorption at 12.09r in the N M R spectrum of ferrocene in strongly acidic media[10], and kinetic
evidence was not at variance with the same conclusion[l]. Cobaltocene, on the other hand, reacted
with acids differently, and also with water to produce the cobalticenium cation [ 11].
Department o f Chemistry I . M . ISSA

Faculty o f Science M . M . ALY*
Assuit University
Assuit, Egypt
*To whom all correspondences should be addressed.
8. M. H. Green, L. Pratt and G. Wilkinson, J. chem. Soc. 3753 (1959).

9. M. Rosenblum, Chemistry o f The Iron Group Metallocenes, Part I, Chap. 2. Interscience, New
York (1965).
10. T. J. Curphey, J. O. Santer, M. Rosenblum andJ. H. Richards, J. Am. chem. Soc. 82, 5249 (1960);
M. L. H. Green, A ngew. Chem. 719 (1960); G. Wilkinson, A ngew. Chem. 35 (1960).
11. G. Wilkinson, P. L. Pauson and F. A. Cotton, J. A m. chem. Soc. 76, 1970 (1954).
J. inorg, nucl. Chem., 1973, Vol. 35, pp. 297-299. Pergamon Press. Printed in Great Britain
The reaction of potassium germyl with boron trimethyl
(Received 10 April 1972)
POTASSIUM germyltrihydroborate, KGeH3BH3, was prepared and characterized in this laboratory [ 1].
Two other germylborates, LiGePh3BPh3[2] and LiGeEt3BPh3[3], are known, and there is evidence
that similar species, KGeH3BX3, are the initial products of reaction between potassium germyl,
KGeH3 and several BX3 compounds (X = I, Cl, OMe)[4]. In this note we describe the reaction
between KGeH3 and boron trimethyl to form the adduct KGeH3BMe3.
1. D.S. Rustad and W. L. Jolly, lnorg. Chem. 7, 213 (1968).

2. D. Seyferth, G. Raab and S. O. Grim, J. org. Chem. 26, 3034 ( 1961 ).
3. E.J. Bulten and J. G. Noltes, J. organometal. Chem. 29, 409 ( 1971 ).
4. C. Riddle and W. L. Jolly. Unpublished observations.

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Notes 295

(D) Effect of azide ion on energy level splittings of nickel( l i ) ion

Table 2. Comparison between some physical para-

Parameter [Ni(H20)n] 2+ [Ni(H20)sN3] +

ZA2~-"* aTz. 8547 cm -1 8696 cm -I

28. Y. Tanabe and S. Sugano, J. phys. Soc., Japan 9, 753 (1954).

The reactivity of cobaltocene as compared to ferrocene

(First received22 November 1971 ; in revised form 12 Apri11972)

1. M. M. Aly, R. Bramely, J. Upadhyay, A. Wassermann and P. Woolliams, Chem. Comm. 404

Department o f Chemistry I . M . ISSA

*To whom all correspondences should be addressed.

8. M. H. Green, L. Pratt and G. Wilkinson, J. chem. Soc. 3753 (1959).

The reaction of potassium germyl with boron trimethyl

(Received 10 April 1972)

1. D.S. Rustad and W. L. Jolly, lnorg. Chem. 7, 213 (1968).

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