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Synthesis of Vinylene-Co,N-Linked Multi(porphyrin)s by the Addition of Free-Base Porphyrins to a C2H2 Complex of Cobalt(III) Porphyrin and Their Oxidative Rearrangement to Vinylene-N,N‘-Linked Multi(porphyrin)s
journal contribution
posted on 1998-04-11, 00:00 authored by Jun-ichiro Setsune, Hirokazu Takeda, Shoji Ito, Yugo Saito, Yoshihiro Ishimaru, Koji Fukuhara, Yasushi Saito, Teijiro Kitao, Tomohiro AdachiThe nucleophilic addition reaction of a pyrrole nitrogen of
free-base porphyrins to a π-complexed acetylene
ligand in a cationic CoIII porphyrin intermediate afforded
good yields of vinylene-Co,N‘-linked
bis(porphyrin)s,
(Por)CoIII−CHCH−(N-Por)H2.
N-substituted porphyrin free bases are N-vinylated
regioselectively at the pyrrole
adjacent to the original N-substituted pyrrole in this reaction.
Tris- and tetrakis(porphyrin)s have been
prepared
by reacting a vinylene-N,N‘-linked
bis(meso-tetraarylporphyrin) with
(OEP)CoIII(H2O)2ClO4
(OEP: octaethylporphyrin dianion) and acetylene. The tetrakis(porphyrin) proved
to be a 1:1 mixture of Ci- and
C2-symmetric
regioisomers. These organometallic CoIII complexes
underwent facile oxidative migration of the Co-bound vinyl
group to a porphyrin pyrrole nitrogen when treated with
FeIII salts or HClO4 to provide moderate to
good yields
of CoII vinylene-N,N‘-linked
multi(porphyrin) complexes.
(Vinylene-N,N‘)bis(porphyrin) free bases
with
combinations of different porphyrins have been obtained by this
procedure. The homobinuclear (2CoII,
2CuII,
and 2ZnII) and heterobinuclear
(CoIICuII and
CoIIZnII) complexes have been prepared and
characterized
spectroscopically. The single-crystal X-ray analysis of
(CHCH-N,N‘)[(OEP)CoIICl][(TPP)ZnIICl]
(TPP: meso-tetraphenylporphyrin dianion) showed a face-to-face structure with an
average inter-ring separation of 4.39 Å
(triclinic P1̄; Z = 2; a =
14.806(4), b = 18.703(10), c =
13.796(3) Å, α = 97.69(3), β = 99.57(2), γ
=
96.74(3)°).
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Keywords
nucleophilic addition reaction2 Zn IIpyrrole nitrogenorganometallic Co III complexesCo II vinyleneTPP2 ClO 4oxidative migrationFe III saltsporphyrin pyrrole nitrogenOxidative Rearrangement4.39 ÅC 2H 2 OCHOEPtetraphenylporphyrin dianionC 2 H 2 Complex2 Cu IIcationic Co III porphyrinCo II Zn IIC iCo II Cu IIHClO 4
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