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The reactions of [(μ-H)3Re3(CO)11(NCMe)] with Sc2@C82- C3 v(8), Sc2C2@C80- C2 v(5), Sc2O@C82- Cs(6), C86- C2(17), and C86- Cs(16) have been carried out to produce face-capping cluster complexes. The Re3 triangles are found to bind to the sumanene-type hexagons on the fullerene surface regiospecifically. In contrast, Sc3N@C78- D3 h(5) and Sc3N@C80- Ih show no reactivity toward [(μ-H)3Re3(CO)11(NCMe)], probably due to electronic and steric factors. These complexes can be easily purified by using HPLC. Carbonylation of each complex releases the corresponding higher fullerene or endohedral metallofullerene in pure form. Remarkably, the C86- C2(17) and C86- Cs(16) isomers were successively separated through Re3 cluster complexation/decomplexation. This unique bonding feature may provide an attractive general strategy to purify as yet unresolved fullerene mixtures. [ABSTRACT FROM AUTHOR]

Abstract: Reaction of C64H4 (1) and Os3(CO)10(NCMe)2 in refluxing chlorobenzene affords (μ-H)Os3(CO)9(μ,η 4-C64H3) (2) and Os(CO)3(η 4-C64H4) (3). Compound 2 apparently arises from C–H bond activation of 1 to generate an η 4-dienyl motif. In contrast, compound 3 is produced by insertion of one osmium atom into a pentagonal ring of 1, together with the Os3 cluster fragmentation. Complexes 2 and 3 have been characterized by IR, NMR, and mass spectroscopies. The structure of 3·C7H8 was determined by a single-crystal X-ray diffraction study. [Copyright &y& Elsevier]

Reaction of W(η2-PhC&z.tbnd6;CPh)3(NMe3) (1) and Ph2PC&z.tbnd6;CPPh2 (dppa) produces W(η2-PhC&z.tbnd6;CPh)3(η1-Ph2PC&z.tbnd6;CPPh2) (2), which contains a pendant phosphine group. Treatment of 2 with W(CO)4(NCMe)2 yields [W(η2-PhC&z.tbnd6;CPh)3](μ,η2-Ph2PC&z.tbnd6;CPPh2)[W(CO)4(NCMe)] (3). Compound 2 reacts with Os3(CO)10(NCMe)2 to afford Os3(CO)10[(μ,η2-Ph2PC&z.tbnd6;CPPh2)W(η2-PhC&z.tbnd6;CPh)3]2 (4), and reacts with Ru3(CO)9(NCMe)3 to afford Ru3(CO)9[(μ,η2-Ph2PC&z.tbnd6;CPPh2)W(η2-PhC&z.tbnd6;CPh)3]3 (5). The crystal structures of 2 and 3 are determined by an X-ray diffraction study. [Copyright &y& Elsevier]

Reaction of W(NCMe)(η2-PhCCPh)3with C60affords W(η3-NC(Me)C60)(η4,η2-C6Ph6) (2) and W(CPh)(NCMe)(η2-C60) (η3,η2-C5Ph5) (3). The hexaphenylbenzene species of 2shows an η4-butadiene + η2-olefin bonding mode and the nitrile carbon is inserted into one 6  5-ring junction of C60. Compound 3contains an η3,η2-pentaphenylcyclopentadienyl and a benzylidyne group from 2 + 2 + 1 cyclization and scission reactions of the diphenylacetylene ligands. [ABSTRACT FROM AUTHOR]

Abstract: Reaction of W(NCMe) (η 2-C2Ph2)3 (1) and PPh2(o-C6H4)C(fluxing toluene affords W(O) (η 3-PPh2(o-C6H4)C5Ph4H) (η 2-C2Ph2) (2). The structure of 2 reveals that an oxygen atom and a pentadienyl group are attached to the tungsten center, apparently arising from activation of the formyl Cd coupling of the diphenylacetylene ligands. [Copyright &y& Elsevier]