Reactions of (η5-C5Me5)Re(NO)(PPh3)(C⋮CLi) with W(CO)6, Fe(CO)5, or Mn(CO)3(η5-C5H
n
Cl
5-n
),
followed by Me3O+ BF4
-, give the heterobimetallic C3OMe complexes (η5-C5Me5)Re(NO)(PPh3)(C⋮CC(OMe))M(CO)
x
(η5-C5H
n
Cl
5-n
)
y
(M/x/y/n = 3, W/5/0/−; 4, Fe/4/0/−; 5, Mn/2/1/5; 6, Mn/2/1/4; 7,
Mn/2/1/0). Spectroscopic and crystallographic (3) data indicate contributions by +ReCCC(OMe)−M-
resonance forms. Reactions of 4−7 and BF3 gas give the title compounds [(η5-C5Me5)Re(NO)(PPh3)(CCC)M(CO)
x
(η5-C5H
n
Cl
5-n
)
y
(M/x/y/n = 9, Mn/2/1/5; 10, Mn/2/1/4; 11, Mn/2/1/0; 12, Fe/4/0/−).
Spectroscopic and crystallographic (9) data indicate dominant contributions by fully cumulated +ReCCCMn
resonance forms. Reactions of (η5-C5Me5)Re(NO)(PPh3)(C⋮CC⋮CLi) with Mn(CO)3(η5-C5Cl5), Mn(CO)3(η5-C5Br5), or Fe(CO)5, followed by Me3O+ BF4
-, give the C5OMe complexes (η5-C5Me5)Re(NO)(PPh3)(C⋮CC⋮CC(OMe))M(CO)
x
(η5-C5X5)
y
(M/x/y/X = 16, Mn/2/1/Cl; 19, Mn/2/1/Br; 20, Fe/4/0/−). However,
Mn(CO)3(η5-C5H5) does not react. Reaction of 16 and BF3 gives the C5 complex [(η5-C5Me5)Re(NO)(PPh3)(CCCCC)Mn(CO)2(η5-C5Cl5)]+ BF4
- (21) as a light-sensitive deep brown powder of
>94% purity. IR and NMR data show a dominant +ReCCCCCMn resonance form. UV−visible
spectra of 9
−
11 and 21 show intense absorptions at 392, 396, 414, and 480 nm (ε 55 800, 50 900, 49 100,
60 500 M-1 cm-1), respectively, and weaker longer wavelength bands. These are believed to have appreciable
rhenium-to-manganese charge-transfer character.
