ISMSC 2007 - Università degli Studi di Pavia

PSB 77
Synthesis, supramolecular architecture and redox properties of cobalt and
iron(II) macrocyclic and macrobicyclic bis- and tris-dioximates with 2,6-ditert-butylphenol
pendants
Yan Z. Voloshin , Dmitrii B. Shpakovsky b , Elena R. Milaeva b , Tatyana V. Magdesieva b ,
Alexander S. Belov a
A. N. Nesmeyanov Institute of Organoelement Compounds, RAS, 119991 Moscow, Russia
E-mail: voloshin@ineos.ac.ru
b
Moscow State Lomonosov University, 119992 Moscow, Russia
The synthesis of coordination compounds with redox-active organic ligands, which are capable
to form stable radical pendants, will be presented.
– e, – H
HO O
+
.
M M
The novel cobalt and iron(II) macrocyclic bis-dioximates (the derivatives of ligand 1) and
macrobicyclic tris-dioximates 2 - 4 with 2,6-di-tert-butylphenol substituents were obtained.
HO
OH
N
N
OH
O
N
N
O
O
F
B
O
N
Fe 2+
N
N N
O
O
B
F
H
HO
S
HO
S B
O O
N
N
M 2+
S S N N N S
S N
O
O
O
O
OH
HO
S B
OH HO
S
1 2 HO 3 HO 4
O
N
S
OH
HO
S
HO
S B
O O
N
N
Fe 2+
O
N
N N
O
O
B
M 2+ = Fe 2+ , Co 2+
From one up to six hindered phenol pendants were incorporated in the cage molecules by the
nucleophilic substitution of the initial reactive chloride clathrochelate precursors with
thiophenolate anion:
N
Fe
N
2+
B
O O O
N
N N
O
O
B O
N H
F
Cl
F
OH
S
.
The pathways and the products of clathrochelates redox transformations in solutions have been
studied using ESR, UV-vis spectroscopy and CVA. The oxidation of phenol-containing
clathrochelates in toluene leads to the formation of stable phenoxyl species.
This work was supported by RFBR ( 05-03-33184, 05-03-32869, 06-03-90903, 06-03-32626
and 07-03-00765).
2
S
S
OH
OH
PSB 78
First synthesis of clathrochelate iron(II) oximehydrazonate with a differ
orientation of the functionalizing substituentes relative to the capping
1,3,5-triazacyclohexane ring
Yan Z. Voloshin , Sergei Y. Erdyakov b , Mikhail E. Gurskii b , Irina G. Makarenko a ,
Ekaterina G. Lebed a , Yurii N. Bubnov a
A. N. Nesmeyanov Institute of Organoelement Compounds, RAS, 119991 Moscow, Russia
e-mail: voloshin@ineos.ac.ru
b
N. D. Zelinsky Institute of Organic Chemistry, RAS, 119991 Moscow, Russia
e-mail: bor@ioc.ac.ru
The H + -ion-catalyzed condensation of the boron-, tin-, antimony- and germanium-containing
semiclathrochelates with an excess of triethyl ortoformate (TOF) results in the formation of the
single clathrochelate product for each of these precursors [1-4]. In case of boron-containing
compounds, the complexes obtained have syn,syn,syn-orientation of the ethoxy groups and
semiclathrochelate fragment relative to the 1,3,5-triazacyclohexane ring, whereas the tin-,
antimony- and germanium-containing clathrochelates molecules have an anti, anti, anticonfiguration.
The macrocyclization of o-carboranyldiboron-capped iron(II) oximehydrazonate
semiclathrochelate with an excess of TOF (Scheme) unexpectedly gives the single
clathrochelate complex with mixed syn, syn, anti-orientation of ethoxy substituents (see X-ray
structure) and with the detachment of one of the two boronate fragments. The unusual antiorientation
of one of the three ethoxy substitutents may be explained by the steric hindered
caused by the second boronate group on the first step of macrocyclization reaction.
H B
Fe 2+
OH
N
NH2 NH2
N N
2+
Fe
N N
N (H3CO) 2B
NH2 N
N
O O O
B
C
NH 2
B(OCH 3) 2
+
C
H +
TOF
CH 3CN
B H
C
B(OCH3) 2
H B
CH 3CN
H C2H5O C2H5O N N
H
N N
2+
Fe
H
OC2H5 N
N
N N N
O
O
B
O
Scheme
This work was supported by RFBR ( 05-03-33184, 06-03-90903, 06-03-32626, 07-03-00765
and 05-03-33268).
[1] Y.Z.Voloshin, O. A.Varzatskii et al., Inorg.Chem.Commun., 1998, 1, 328-331
[2] Y.Z.Voloshin, A.I.Stash et al., Inorg.Chim.Acta, 1999, 284, 180-190
[3] Y.Z.Voloshin, O. A. Varzatskii et al., Inorg.Chim.Acta, 2000, 299, 104-111
[4] Y.Z.Voloshin, O.A. Varzatskii et al., Inorg. Chim. Acta, 2004, 357, 3187-3204
C
+
H H
H