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CHEMICAL COMMUNICATIONS,
1968
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Organic Derivatives of a Cobalt(111) Macrocylic Complex
By EI-ICHIRO OCHIAIand DARYLE
(Department of Chemistry, The Ohio State University, Columbus, Ohio 43210)
SEVERALof the reported model complexes of
vitamin B,,, contain cobalt-carbon o-bonds. One
of them, alkylcobaltoxime, RCo dmg,L,1 (R =
alkyl or analogous group, dmg = dimethylgly-
oxime, 1, = base, e.g. water or pyridine) has been
studied in detail. These investigations have dealt
with the synthesis, chemical characteristics, bio-
chemical implications, and nucleophilicity of
cobalt(1) in the complex.2 Other examples in-
clude RCo baen,3 RCo ~ a l e nand
, ~ RCo(porphyrin),5
905
H. BUSCH*
[baen = bis(acetylacetone)ethylenediamine, salen
= bis(salicylaldehyde)ethylenediamine]. We re-
port the synthesis of a new model complex of
the general formula [RCoIII cyp Br]Y {R = alkyl or
analogous groups, cyp = 2,12-dimethy1-3,7,11,17-
tetra-azabicyclo [11,3,l]heptadeca-l(17),
2,11,13,15-
pentaene (I)}.
The general method of preparation involves the
reduction of CoII cyp Br,,H,O with sodium boro-
hydride in the presence of an alkyl halide, or its
analogue, under nitrogen in methanol. The
compound is crystallized by the addition of an
aqueous solution of ammonium hexafluorophos-
phate. Complexes [MeCo cyp Br]PF6, [EtCo cyp-
Br]PF,,QH,O, and [CH, :CHCO cypBr]PF,,+H,O
gave satisfactory elemental analysis. Molar con-
ductances, in methanol, a t concentrations of ca.
7 x 1 0 - 4 ~fall in the range 109-114mho/cni.2.
This shows that these compounds are 1 :1 electro-
lytes.6 The i.r. spectra show the typical cyp
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906 CHEMICALCOMMUNICATIONS,
1968
skeletai bands, as observed for [CoIII cyp X,]YJ7 existence of the bonding orbital composed of the
Published on 01 January 1968. Downloaded by University of Massachusetts - Amherst on 26/10/2014 20:35:23.

where X and Y are halogens or analogues. The cobalt dz2 and the carbon a-orbital a t a relatively
spectrum of [CH, :CHCo cypBr]+ shows an high level, i.e., just below the d-orbitals. An
absorption band due to the C =C stretching mode a t electron in this orbital is readily excited into the
1608 cm.-l. vacant antibonding orbital composed mainly of
The electronic spectra of these complexes dzg; this transition corresponds to the charge
resemble those of approximately octahedral transfer CoTII+-R-. This results in the decom-
cobalt(II1)complexes. They consist of two bands : position of the complex into a CoII derivative and
IT,, + lA,,, ca. 480 and lT,, t lAlg, ca. 390 mp. an alkyl radical, as shown by Schrauzerl in the case
However, the intensities of these bands are fairly of RCo dnig,L complexes.
large, E 600-2000, compared with the ordinary Evidence also exists for the compounds [PhCH,*-
octahedral cobalt(rI1) complexes. This is con- CocypBrIPF, [6(CH) benzyl a t 739 and 695
sistent with the expectation of a considerable cm.-l], [NCCH,CH,Co cypBr]PF, [v(C=N) a t
amount of covalency in the bond between CoIII 2240 cm.-l] and [ClCH,-Co cypBr]PF,. The
(probably dz2 orbital) and the carbon atom. These benzyl derivative is very sensitive to light, probably
spectra are similar to that of EtCo dmg, py (py = because of the stability of benzyl radical. The
pyridine) which has bands a t 448 (E 1210) and 380 formation reaction of the ally1 derivative proceeds
mp ( E 1760).? in close similarity to the other cases, but this
These complexes are photo-labile in solution as substance is so reactive that no solid product has
are RCo dmg,L, RCo baen, and RCo salen. Simple yet been isolated.
molecular orbital considerations suggest the (Received, May 30th, 1968; Com. 703.)
t This complex was prepared by a method similar to that of Schrauzer et aZ.1 and its spectrum was obtained in the
present study.
G. N. Schrauzer, Accounts Chem. Res., 1968, 1, 97 and references cited therein.
G. N. Schrauzer, E. Deutsch, and R. J. Windgassen, J . Amer. Chem. Soc., 1968, 90, 2441.
G. Costa and G. Mestroni, J . 0.vganometallic Chem., 1968, 11, 325.
G.Costa, G.Mestroni, and G. Pellizer, J . OrganometaZZic Chem., 1968, 11, 333.
D. A. Clarke, R. Grigg, and A. W. Johnson, Chem. Comm., 1966, 208.
ti E. C. Evers and A. K. Gnox, J . Amer. Chem. SOG., 1951,73, 1739; R. E. Jervis, D. R. Muir, J. P. Butler, and
A. R. Gordon, ibid., 1953, 75, 2855.
' I(. M. Long, Ph.D. Thesis, The Ohio State University, 1967.