Cyanide ion as a four-electron donating bridging ligand in a dimanganese compound
- 1 January 1983
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 12,p. 2669-2671
- https://doi.org/10.1039/dt9830002669
Abstract
Reaction of [Mn2(CO)5(dppm)2](dppm = Ph2PCH2PPh2) with HBF4·Et2O in the presence of acetonitrile gives the complex [Mn2H(CO)5(NCMe)(dppm)2][BF4] which reacts with cyanide ion to give [Mn2H(CN)(CO)5(dppm)2], shown by 1H, and 13C (90% enriched 13CN) n.m.r. to contain a terminal cyanide ligand. Decarbonylation with Me3NO·2H2O gives [Mn2H(CN)(CO)4(dppm)2], n.m.r. spectra of which at –90 °C are consistent with an asymmetrically bridging CN, probably C-bonded at one Mn atom and η2-bonded at the other. The 13C n.m.r. signal with coupling to 31P changes from a 1 : 4 : 6 : 4 : 1 quintet (J= 10.8 Hz) at 25 °C to a 1 : 2 : 1 triplet (J= 22.1 Hz) at –90 °C because the CN group is oscillating between the two metal atoms.Keywords
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