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Mononuclear Mn(III) complexes with water
- Mn(phen)(OH2)Cl3, [Mn(acac)2(OH2)]ClO4.2H2O - comparison of Jahn-Teller
active d4 polyhedron with the isostructural (inactive) d5 polyhedron -
MnO(OH) as a source of Mn(III): G. Swarnabala, K. R. Reddy,
J. Tirunagar and M. V. Rajasekharan Trans. Met. Chem. 19, 506-508(1994).
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Bis-chelate of Mn(III) with phen - [Mn(phen)2Cl2]NO3. 2.5H2O - disproportionation-dimerisation
and "16-line" EPR : K. R. Reddy and M. V. Rajasekharan Polyhedron
13, 765-769(1994); G. Swarnabala and M.V. Rajasekharan Inorg. Chim.
Acta 168, 167-168(1990).
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The ceric route - disproportionation/proton-coupled
e-transfer - to high valent Mn - [Mn2(III,III)O(OAc)2(H2O)(NO3)(bpy)2]ClO4.CH3COOH,
[Mn2(IV,IV)(O)2(OAc)(H2O)2(bpy)2](ClO4)3.H2O, Mn3(IV,IV,IV)(O)4(phen)4(H2O)2](NO3)4.
2.5H2O - different Jahn-Teller modes in Mn2(III,III)O(OAc)2(2+)
core. The above Mn2(IV,IV)(O)2(OAc)(3+) and the isostructural
[Mn2(III,IV)(O)2(OAc)(H2O)2(bpy)2] (ClO4)2.HNO3 have
the weakest magnetic couplings among all the known Mn(III,IV) and Mn(IV,IV)
complexes : K. R. Reddy, M. V. Rajasekharan and S. Sukumar
Polyhedron
15, 4161-4168(1996); K. R. Reddy, M. V. Rajasekharan, S. Padhye, F. Dahan
and J.-P. Tuchagues Inorg. Chem. 33, 428-433(1994); K. R. Reddy,
M. V. Rajasekharan, N. Arulsamy and D. J. Hodgson Inorg. Chem. 35,
2283-2286(1996).
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Oxygen evolution from water/Ce(IV)(NO3)6(2+)-Mn(III,IV)-
heterogeneous phase - polymers and gel give larger turnover numbers. A
water stable Mn(III,IV) complex - [Mn2(III,IV)(O)2(bpy)4]Ce(III)(NO3)6.
4H2O with a H-bonded lattice water - static disorder - role of the
Jahn-Teller distortion, trans effect and H-bonding on the disorder
direction : G. Swarnabala and M. V. Rajasekharan Proc.
Indian Acad. Sci. (Chem. Sci.) 102, 87-98(1990); D. Ramalakshmi
and M. V. Rajasekharan Acta Cryst. B55, 186-191(1999).
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Mn with non-innocent ligands - Mn(SBQ)2
- what is the difference between the S=1/2 ground
states derived from a low spin Mn(II) bound to diamagnetic form of the
ligands on the one hand, and a doublet state resulting from strong antiferromagnetic
coupling between a Mn(IV) ion bound to the radical form of the ligands,
on the other? - single crystal EPR studies : G. Swarnabala,
M. V. Rajasekharan and S. Padhye Chem. Phys. Lett. 267, 539-544(1997).
Mn(III)-Schiff base-pseudohalide polymers
and Fe analogs
______________________________________________________________________________________________
ligands : acacH = acetylacetone; bpy = 2,2’-bipyridine;
phen = 1,10-phenanthroline; SBQ = 3,5-di-tert-butyl-1,2-quinone-1-(2-oxo-3,5-di-tert-butyl-3,6-cyclohexadiene)imine
radical.
Silver(I,II)
Copper(II)
Polyiodides
Polymeric compounds
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![[Mn2(III,IV)(O)2(bpy)4]Ce(III)(NO3)6. 4H2O with a H-bonded lattice water](mnce.gif){kind=link}