c6() cocrystallises with ferrocene t o give black C60(ferrocene)2, which contains discrete CEO and ferrocene molecules; the ferrocene does not reduce CeO, but the structure appears t o be stabilised as a result of weak intermolecular cha rg e-t ra nsfer i nte ractions.Buckminsterfullene (c60) is a molecular building block, which can be used to prepare new materials with interesting properties.1-3 It behaves as a mild oxidising agent, displaying six reversible one-electron reductions in solution,4 and may be described as a partly delocalised electrophilic poly-alkene. As an electron acceptor, c 6 0 can be expected to interact with electron-donors (D) to form either charge-transfer complexes, C60Dn, or charge-separated systems, [C,.-][D+],,. The extent of charge separation has important bearing on the preparation of molecular conductors and soft ferromagnets.235 Discrete c 6 0 molecules have been successfully incorporated into novel ionic and molecular materials. For example, alkali metal 'salts', C60Mn (n = 3, 4, 6) have been prepared and (n = 3) display high temperature superconductivity.2 c 6 0 is an ideal guest for a-, por y-cyclodextrin [especially the latter, with which it forms a water-soluble, encapsulated complex, Cm(y-cyclodextrin)2] .6 Analogous behaviour was not observed with the larger oblate spheroidal fullerene, C70. c 6 0 also cocrystallises with 1 ,Chydroquinone to yield a solid, formulated as C60( 1,4-hydroq~inone)3,~ which consists of a polymeric hydrogen-bonded lattice containing large cavities occupied by the c 6 0 molecules. The stability of this compound is

Reaction of c6&& with benzene/FeCI3 yields C60Ph5CI which is readily reduced t o C60Ph5H, the main product of reacting c 6 0 with BrJFeCIdbenzene; both compounds have been characterised by NMR spectroscopy.The sp2-hybridised carbon framework and the associated cage strain makes [60]fullerene a potent electrophile.1 [60]Fullerene appears to be more electrophilic than [70]fullerene, as indicated by the IH resonances in the NMR spectra of hydrogenated [60]fullerenes lying considerably downfield from those for hydrogenated [70]fullerenes2~3 and by the equilibrium constants for reaction of [a]and [70]-fullerenes with N,N-dime t hylaniline .4We showed previously that C60Ph12 was amongst the products obtained in electrophilic substitution of benzene by [60]fullerene in the presence of Br2/FeC13.5 Friedel-Crafts reaction of polychlorinated [60]fullerenes with benzene gave products containing up to 22 phenyl groups.6 We have now isolated some 10 products (some as yet uncharacterised) from the former reaction, find that the main product is CmPhSH, and that this is also formed by reacting CmCl6 (which we described recently)7 with benzene/FeC13 followed by reduction.CmPh5C1 was prepared by heating CmCl67 with benzene-FeCI3 for 20 min, cooling, washing the benzene layer with water, separating and drying (MgS04). The residue obtained after benzene removal was set aside to crystallise from carbon tetrachloride, and gave translucent orange crystals (68%). These crystals contain CC14 trapped in the lattice, for on heating to ca. 80 "C they become opaque, the loss of CC14 was also monitored by IR spectroscopy. The mass spectrum (Fig. 1, EI, heated DCI probe), the first obtained for a chlorinated fullerene, confirmed the molecular formula as CmPh5C1. The

No abstract

The catalytic disproportionation of H2O2 to O2 and H2O is achieved with the asymmetric hemerythrin model complex 1, which has a reactive coordination site. The catalytic cycle proceeds via the oxyhemerythrin form with a coordinated hydrogenperoxo ligand. L  1,4,7‐trimethyl‐1,4,7‐triazacyclononane, bpy  2,2′‐bipyridine. equation image

The preparation and characterisation of [ MnL1(CH,CO,),] (I), [Mn6(p,,(C6H,C0,)lo(, [FeL'CI,] (lo), [FeCCI,] (2), and [Fe,L1,(p-O){p-(CH,),CCO,},] [CIO,], (3) are reported where L1 and L2 are bis( benzimidazol-2-ylmethy1)amine and bis( benzimidazol-2-ylmethyl)methylamine. The molecular structures of ( l ) , (2), and (3) were determined b y X-ray diffraction. Complex (1) exists as a discrete, neutral, mononuclear species in the solid state. The manganese(ii) ion is five-coordinate with the tridentate ligand bound in a meridional manner. Both acetates are monodentate with Mn-0 distances of 2.076(5) and 2.1 58(5) A. Complex (9) contains a [Mn6(p4-O),]'o+ core, formally 4 M n " : 2Mn! Complex ( 2) is neutral, mononuclear, distorted octahedral. The ligand co-ordinates in a similar manner to that seen in ( 1) and the chlorides occupy the three remaining meridional sites, with Fe-Cl(equatoria1) 2.31 8(5) A and Fe-CI(axia1) 2.322(5) and 2.433(5) A. The Mossbauer spectrum of (10) at room temperature comprises a quadrupole doublet: 6 = 0.40(1), A€Q = 0.33(2) mm s? Complex (3) is a dinuclear iron(iit) species containing the triply bridged [Fe,(p-0) (p-RCO,),]" core. The Fe Fe distance is 3.075(5) A and the Fe-O(oxo)-Fe angle is 11 7.0(6)". The high-spin iron(iii) centres are antiferromagnetically coupled with J = -1 16 cm-l.