Fullerene complexes synthesis

Rubin, Y. Parker, T.C. Kahn S.I. Holliman, C.L. McElvany S.W. Precursors to endohedral metal fullerene complexes synthesis and x-ray structure of a flexible macrocyclic acetylenic cyclophane CgiH h- J. Am. Chem. Soc. 1996, 35(22), 5308-5309. 

The possibility of this binding mode was shown recently with the synthesis and structural analysis of the dumbbell-shaped bis-fullerene complexes of molybdenum and timgsten. The X-ray crystal structure proves the (71 -0 0)21 1 binding mode (Figure 7.9) [87]. 

FT-ICR, see Fourier-transform ion cyclotron resonance Fullerene[60], germanium-germanium addition, 10, 748 Fullerenes with cobalt, 7, 51 on cobalt Cp rings, 7, 73 inside metallodendrimers, 12, 401 microwave applications, 1, 334 Pd rc-complexes, 8, 348 Ru—Os complexes, 6, 830 with tungsten carbonyls, 5, 687 )2-Fullerenes, with platinum, 8, 634 Fulvalene actinide complex, synthesis, 4, 232 Fulvalene chromium carbonyls, synthesis and characteristics, 5, 264... 

A common route to the synthesis of fullerene complexes is by displacement of other ligands, typically those weakly coordinated to metals. Examples of such ligands include ethylene (equation 6.14) and CH3CN (equation 6.15). 

The synthesis of fullerene complexes of Pd was developed following precedents with Pt. Complexes C6oPd(PR3)2 and C6o (Pd(PR3)2)6 (R=Ph, Et, PMe2Ph, PPh2Me, or P(OMe)3) were soon prepared/ " and studied with a number of techniques such as electrochemistry and Raman spectooscopy. The Raman spectra demonstrated a reduction in symmetry from in the unsubstituted C6o. to C2V in (7/ -C6o)Pd(PR3)2, and to Th in C6Q (Pd(PR3)2)6. As a consequence, some vibrational modes which are silent in Ceo become active upon coordination, and some degenerate vibrational modes are split. 

Diederich F, Jonas U, Gramlich V, Herrmann A, Ringsdorf H and Thilgen C 1993 Synthesis of a fullerene derivative of benzo[18]crown-6 by Diels-Alder reaction complexation ability, amphiphilic properties, and x-ray crystal structure of a dimethoxy-1,9-(methano[1, 2]benzomethano)fullerene[60] benzene clathrate Helv. Chim. Acta 76 2445-53... 

Maggini M, Done A, Scorrano G and Prato M 1995 Synthesis of a [60]fullerene derivative covalently linked to a ruthenium (II) tris(bipyridine) complex J. Chem. Soc., Chem. Commun. 845-6... 

Fullerenes can be considered as a molecular full stop to organic synthesis highly complex and possibly very useful molecules are formed by self-organization of carbon atoms in the vapor phase. Sometimes synthetic chemists are not needed. 

A review9 with more than 37 references includes an examination of symmetry groups and chirality conditions for C60 and C70 bonded to one or two metals in rf and/or rf fashion. Palladium and platinum rf complexes of C6o and C70 are described (novel synthesis, NMR spectra, electrochemistry) as well as first optically active organometallic fullerene derivatives. 

A methanofullerene derivative possessing an ammonium subunit has been prepared and subsequently shown to form a supramolecular complex with a porphyrin-crown ether conjugate <06T1979>. The synthesis and study of these fullerene-containing supramolecular photoactive devices have also been reported <06CRC1022>. 

J.-P. Bourgeois, P. Seiler, M. Fibbioli, E. Pretsch, F. Diederich, L. Echegoyen, Cyclophane-Type Fullerene-dibenzo [18] crown-6 Conjugates with trans-1, trans-2, and trans-3 Addition Patterns Regioselective Templated Synthesis, X-ray Crystal Structure, Ionophoric Properties, and Cation-Complexation-Dependent Redox Behavior , Helv. Chim Acta 1999, 82,1572-1595. 

Klumpp C, Lacerda L, Chaloin O, Da Ros T, Kostarelos K, Prato M, Bianco A (2007) Multifunctionalised cationic fullerene adducts for gene transfer Design, synthesis and DNA complexation. Chem. Commun. 3762-3764. 

Braun T, Buvari-Barcza A, Barcza L, Konkoly-Thege I, Fodor M, Migali B (1994) Mechanochemistry a novel approach to the synthesis of fullerene compounds. Water soluble Buckminster fullerene - gamma- cyclodextrin inclusion complexes via solid-solid reaction. Solid State Chem. 74 47-51. 

Reaction of 217 with Cjq leads to the amino-protected porphyrin-fulleropyrroli-dine, which can easily be deprotected to the corresponding amine [229, 277]. By further functionalization via amide coupling an easy access to extended donor-acceptor systems is possible. A carotene-porphyrin-fullerene triad was prepared by reaction of the amine with the appropriate carotene acid chloride. The motivation for the synthesis of all these donor-acceptor systems is the attempt to understand and imitate the photosynthetic process. On that score, a model for an artificial photosynthetic antenna-reaction center complex has been achieved by attaching five porphyrin cores in a dendrimer-like fashion to the fullerene [242]. 

The smallest subimit of these fullerene polymers is the C j2o dimer [368], Synthesis and examination of the properties of this molecule are, therefore, of considerable interest. Beside the solid-state mechanochemical reaction of with KCN -described in Section 3.2.3 -the dimer Cj2o can be synthesized at 5 GPa and 200 °C in good yields from a bis(ethylene-difhio)TTF-C5Q complex [369]. Cj2o is a dark brown solid that is almost insoluble in most organic solvents. 1 ts solubility decreases with increasing purity of the sample this behavior is also known for pristine C q. 

Since the first report of a complex involving a direct metal-to-Ceo bond, (Ph3P)2 Pt( 7 -C6o)/ numerous studies have established that the fullerene Ceo acts as a moderately electronegative alkene in coordinating to electron-rich metal centers. In many cases the Ceo ligand is subject to relatively facile displacement when the complex is in solution however, the zerovalent, octahedral complexes M(CO)3(dppe)(Cgo) [M = Mo, W dppe = l,2-bis(diphenylphosphino)ethane] display outstanding stability even under severe conditions. The overall time needed to prepare these complexes from commercially available M(CO)g is dramatically reduced by adopting a biphasic procedure for the synthesis of the precursor M(CO)4(dppe), which was first described for the preparation of Mo(CO)4 (dppe). Here details are presented for the biphasic synthesis of W(CO)4(dppe) and for its use in the preparation of W(CO)3(dppe)(Cgo)-... 

The synthesis and structures of transition metal complexes of anionic cyclo-polypnictogen ligands, e.g. cyclo-P5, are discussed in Section 7.2.1 and 11.2. An exciting recent development involves the use of these complexes as building blocks for the construction of novel supramolecular assemblies, including one-dimensional (ID) and two-dimensional (2D) polymers and even soluble spherical fullerene-like aggregates.Complexes that have been used for this... 

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