An Open-Cage Fullerene That Mimics the C H (5,5)-Carbon Nanotube Endcap to Host Acetylene and Hydrogen Cyanide Molecules.

Treatment of the open-cage fullerene C H NO (Ph) (Py)(N C H ) (1) with methanol at 150 °C results in an orifice-enlargement reaction to give C H NO(CO Me)(Ph)(Py)(N C H ) (2). The overall yield from C to isolated 2 is 6.1 % (four steps).

Encapsulation of Formaldehyde and Hydrogen Cyanide in an Open-Cage Fullerene.

Reaction of C63 NO2 (Ph)2 (Py) (1) with o-phenylenediamine and pyridine produces a mixture of C63 H4 NO2 (Ph)2 (Py)(N2 C6 H4 ) (2) and H2 O@2. Compound 2 is a new open-cage fullerene containing a 20-membered heterocyclic orifice, which has been fully characterized by NMR spectroscopy, high-resolution mass spectrometry, and X-ray crystallography. The elliptical orifice of 2 spans 7.

The Solitary Isomer of C60 H18 Is Proven to Have a C3v Crown Shape: Crystal Structure Determination and Synthesis of Its Triruthenium Cluster Complex.

Analytically pure C60 H18 is obtained by a Ru3 cluster complexation and decomplexation method. The crystal structure of C60 H18 consists of one flattened hemisphere, to which all 18 hydrogen atoms are symmetrically bonded, and one curved hemisphere akin to C60 . A benzenoid ring in the flattened hemisphere is isolated from the residual π systems by a belt composed of sp(3) -hybridized CH units.

Regiospecific coordination of Re(3) clusters with the sumanene-type hexagons on endohedral metallofullerenes and higher fullerenes that provides an efficient separation method.

The reactions of [(μ-H)3 Re3 (CO)11 (NCMe)] with Sc2 @C82 -C3v (8), Sc2 C2 @C80 -C2v (5), Sc2 O@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, Sc3 N@C78 -D3h (5) and Sc3 N@C80 -Ih show no reactivity toward [(μ-H)3 Re3 (CO)11 (NCMe)], probably due to electronic and steric factors.

Activation of open-cage fullerenes with ruthenium carbonyl clusters.

Reactions of the open-cage fullerene C63NO2(Py)(Ph)2 (1) with [Ru3(CO)12] produce [Ru3(CO)8(μ,η(5)-C63NO2(Py)(Ph)2)] (2), [Ru2H(CO)3(μ,η(7)-C63N(Py)(Ph)(C6H4))] (3), and [Ru(CO)(Py)2(η(3)-C63NO2(Py)(Ph)2)] (4), in which the orifice sizes are modified from 12 to 8, 11, and 15-membered ring, through ruthenium-mediated C-O and C-C bond activation and formation.

Functionalization of the tetrairon cluster Cp4Fe4(CO)4 with fulleropyrrolidine.

Condensation of the formyl group of Cp3Fe4(CO)4(C5H4CHO) with N-methylglycine and C60 produces Cp3Fe4(CO)4(C5H4-CHNMeCH2C60) (1), where one cyclopentadienyl ring of the tetrairon cluster is linked to a fulleropyrrolidinyl moiety. A similar reaction with the bisformyl cluster Cp2Fe4(CO)4(C5H4CHO)2 affords Cp2Fe4(CO)4(C5H4-CHNMeCH2C60)2 (2). Compounds 1 and 2 have been characterized by mass, IR, UV-Vis, and NMR spectroscopy.

Re-Re bond breaking of (μ-H)3Re3(CO)11(NCMe) upon reaction with PPh2(o-C6H4)(CH2NMeCH)C60 to generates monorhenium and dirhenium phosphino-fullerene complexes.

Reaction of PPh(2)(o-C(6)H(4))(CH(2)NMeCH)C(60) (1) and (μ-H)(3)Re(3)(CO)(11)(NCMe) in refluxing chlorobenzene affords the monorhenium complex HRe(CO)(3)(η(3)-PPh(2)(o-C(6)H(4))(CH(2)NMeCH)C(60)) (2), and the dirhenium complexes (μ-H)Re(2)(CO)(7)(μ,η(3)-PPh(o-C(6)H(4))(2)(CH(2)NMeCH)C(60)) (3) and (μ-H)Re(2)(CO)(5)(μ-SSOH)(μ,η(5)-PPh(2)(o-C(6)H(4))(CH(2)NMeCH)C(60)) (4). The structures of 2-4 have been determined by an X-ray diffraction study. The oxatrisulfanyl (-SSOH) ligand of 4 likely arises from decomposition of CS(2) on silica gel during the purification processes.

[(μ-H)3Re3(CO)9(η2,η2,η2-Sc2C2@C(3v)(8)-C(82))]: face-capping cluster complex of an endohedral fullerene.

Like a miniature trophy, the complex pictured was obtained as the sole product from the reaction of Sc(2)C(2)@C(3v)(8)-C(82) and [(μ-H)(3)Re(3)(CO)(11)(NCMe)] and characterized by IR, visible/near-infrared, and NMR spectroscopy, mass spectrometry, and X-ray diffraction. Coordination of the Re(3) cluster to the unique hexagon oriented perpendicular to the C(3) axis of the fullerene core altered the geometry and electronic properties of Sc(2)C(2)@C(3v)(8)-C(82).

Synthesis of the phosphino-fullerene PPh2(o-C6H4)(CH2NMeCH)C60 and its function as an η1-P or η3-P,C2 ligand.

Following the method of Prato et al., reaction of C(60), N-methylglycine and o-(diphenylphosphino)benzaldehyde affords PPh(2)(o-C(6)H(4))(CH(2)NMeCH)C(60) (1) in moderate yield. Compound 1 reacts with W(CO)(4)(NCMe)(2) to produce W(CO)(4)(η(3)-PPh(2)(o-C(6)H(4))(CH(2)NMeCH)C(60)) (2), through coordination of the phosphine group and one 6 : 6-ring junction of fullerene.

C60-induced alkyne-alkyne coupling and alkyne scission reactions of a tungsten tris(diphenylacetylene) complex.

Reaction of W(NCMe)(η(2)-PhC≡CPh)(3) with C(60) affords W(η(3)-NC(Me)C(60))(η(4),η(2)-C(6)Ph(6)) (2) and W(≡CPh)(NCMe)(η(2)-C(60)) (η(3),η(2)-C(5)Ph(5)) (3). The hexaphenylbenzene species of 2 shows an η(4)-butadiene + η(2)-olefin bonding mode and the nitrile carbon is inserted into one 6:5-ring junction of C(60). Compound 3 contains an η(3),η(2)-pentaphenylcyclopentadienyl and a benzylidyne group from 2 + 2 + 1 cyclization and scission reactions of the diphenylacetylene ligands.

Coordination of NO(2)(-) ligand to Cu(I) ion in an O,O-bidentate fashion that evolves NO gas upon protonation: a model reaction relevant to the denitrification process.

[(2,6-(Ph(2)P(o-C(6)H(4))CH=N)(2)C(5)H(3)N)(2)Cu(2)](BF(4))(2) (2) has been prepared by treating 2,6-(Ph(2)P(o-C(6)H(4))CH=N)(2)C(5)H(3)N (1) with [Cu(NCMe)(4)]BF(4). Reaction of 2 and [Ph(3)PNPPh(3)]NO(2) produces (2,6-(Ph(2)P(o-C(6)H(4))CH=N)(2)C(5)H(3)N)Cu(NO(2)) (3), with the nitrite ligand in a unique eta(2)-O,O coordination mode. Protonation of 3 releases NO gas, which mimics the reactivity of the Type 2 Cu-NiRs.

Reactions of Triosmium Carbonyl Clusters with Thionylaniline. Crystal Structures of Os(3)(CO)(9)(&mgr;(3)-NPh)(&mgr;(3)-S), Os(3)(CO)(9)(&mgr;(3)-eta(2)-(PhN)(2)SO)(&mgr;(3)-S), and Os(3)(CO)(8)(NCMe)(&mgr;(3)-NPh)(&mgr;(3)-S).

Reaction of Os(3)(CO)(12) with thionylaniline (PhN=S=O) in refluxing methylcyclohexane produces Os(3)(CO)(9)(&mgr;(3)-NPh)(&mgr;(3)-S) (1) in good yield. When Os(3)(CO)(10)(NCMe)(2) is treated with PhN=S=O at room temperature, compound 1 and Os(3)(CO)(9)(&mgr;(3)-eta(2)-(PhN)(2)SO)(&mgr;(3)-S) (2) result. Compound 1 reacts with trimethylamine oxide in the presence of acetonitrile to give Os(3)(CO)(8)(NCMe)(&mgr;(3)-NPh)(&mgr;(3)-S) (3).