Treatment of fullerenes with reducing metals and a
proton source leads to the formation of
hydrogenated fullerenes (C60H
n
and
C70H
n
). The reaction of
C60 with a variety of metals was
investigated, using metals that span a broad range of reducing power,
from tin (E° = −0.14 V) to
magnesium (E° = −2.36 V). We report useful
synthetic routes to a number of reduced fullerenes,
including C60H2, C60H4,
and C60H6, and we have determined that, despite
the huge number of isomers
that are possible, a small number are actually formed in these cases.
For example, only two isomers
of C60H6 are obtained in the Zn(Cu) reduction
of C60, in a 6:1 ratio. Three isomers of
C70H10 are
produced, in ratios that are dependent on reaction time.
Ph(Cl)2Al«P(SiMe3)3 (V) was isolated from the reaction of equimolar amounts of PhAlCl2 and P(SiMe3)3. Compounds I-V were characterized by NMR spectroscopy and partial elemental analysis. In addition, the solid-state structures of I-III were determined by single-crystal X-ray analysis. Compound I crystallizes in the monoclinic space group P2\ln (C2A 5 ), while H crystallizes in the triclinic space group P UQ 1 ), each with two discrete molecules per asymmetric unit. Crystals of compound III belong to the orthorhombic space group P2i2i2i(D2 4 )-Compounds I-III are the first structurally-characterized compounds to contain phenyl-substituted Al centres bonded to heavier pnicogen atoms.
The reactions of trimethylaluminum with diphenylarsine, Ph 2 AsH, and phenyl [(trimethylsilyl)methyl]arsine, Ph(Me 3 SiCH 2 )AsH, in 1:1 mole ratios afford the trimeric compounds [Me 2 AlAsPh 2 ] 3 ‚(C 7 H 8 ) 2 (1) and [Me 2 AlAs(CH 2 SiMe 3 )Ph] 3 (2), respectively. Compounds 1 and 2 are the first Al-As six-membered-ring compounds to be structurally characterized by singlecrystal X-ray crystallography, as well as by 1 H and 13 C solution NMR spectroscopy. X-ray crystallographic analysis revealed that trimer 1 is a toluate that crystallizes in the monoclinic space group P2 1 /n, with a ) 14.549(6) Å, b ) 22.838(7) Å, c ) 16.891(4) Å, and β ) 105.12(5)°f or Z ) 4. Trimer 2 crystallizes in the triclinic system, space group P1 h, and has two unique molecules in a unit cell with dimensions of a ) 15.619(7) Å, b ) 17.487(6) Å, c ) 19.863(6) Å, R ) 94.86(3)°, β ) 101.41(3)°, and γ ) 113.34(3)°for Z ) 4. The six-membered Al-As rings in both 1 and 2 occupy chair conformations, furnishing both trimers with structural characteristics similar to those of cyclohexane. The Al and As centers of both 1 and 2 reside in pseudotetrahedral environments, with the Al-As bond lengths ranging from 2.512(3) to 2.542(3) Å in 1 and from 2.504(5) to 2.526(5) Å in 2.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.