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New forms of coordinated carbon: Wirelike cumulenic C3 and C5 sp carbon chain that span two different transition metals and mediate charge transfer.

Autorzy

T. Bartik

W. Weng

J. A. Ramsden

Sławomir Szafert

S. B. Falloon

A. M. Arif

John A. Gladysz

Rok wydania

1998

Czasopismo

Journal of the American Chemical Society

Numer woluminu

120

Strony

11071-11081

DOI

10.1021/ja981927q

Kolekcja

Naukowa

Język

Angielski

Typ publikacji

Artykuł

Streszczenie

Reactions of (η5-C5Me5)Re(NO)(PPh3)(C⋮CLi) with W(CO)6, Fe(CO)5, or Mn(CO)3(η5-C5HnCl5-n), followed by Me3O+ BF4-, give the heterobimetallic C3OMe complexes (η5-C5Me5)Re(NO)(PPh3)(C⋮CC(OMe))M(CO)x(η5-C5HnCl5-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-C5HnCl5-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.

Adres publiczny

https://doi.org/10.1021/ja981927q

Strona internetowa wydawcy

https://www.acs.org/content/acs/en.html

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