From the reaction of
[Ru2Cl3(PMe2Ph)6]
Cl with the appropriate radical anions, yellow complexes of general formula
[Ru(PMe2Ph)3(η4-arene)]
[arene = naphthalene
(C10H8) (1), anthracene
(C14H10) (2), and triphenylene
(C18H12) (3)] have been
isolated in poor yield and characterized by elemental analysis, n.m.r.
(1H, 13C,
31P) spectroscopy and single-crystal X-ray diffraction.
Crystal data: (1), monoclinic,
C2/c, a
31.096(8), b 12.012(4), c
17.078(8) Å, β 104.41(3)˚, V 6178(4)
Å3, ? 8, refined to
final R value of 0.032 with use of 3641 reflections
[I > 3σ(I)];
(2), monoclinic, C2/c,
a 55.909(4), b 14.348(5),
c 17.573(5) Å, β 105.41(1)˚,
V 13590(6) Å3,
Z 16 (two molecules per asymmetric unit), refined to
final R value of 0.049 with use of 7770 reflections
[I > 3σ(I)]; (3), mono-clinic,
Pn, a 9.377(3),
b 12.229(3), c 15.975(3) Å,
β 103.51(2)˚, V 1781.2 (7) Å3,
Z 2, refined to final R value of
0.026 with use of 2830 reflections [I >
3σ(I)]. In each case, coordination of the
zerovalent metal fragment
Ru(PMe2Ph)3 to the diene section
of one of the terminal rings causes the aromatic molecule to be folded by
c. 40˚ at the outer carbon atoms of the diene. The
coordination geometry about ruthenium is approximately square pyramidal, with
the diene and two tertiary phosphines in the equatorial plane and the
remaining tertiary phosphine in the axial site.
Influence of the Oxygen Atom Acceptor on the Reaction Coordinate and Mechanism of Oxygen Atom Transfer From the Dioxo-Mo(VI) Complex, TpiPrMoO2(OPh), to Tertiary Phosphines