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Alkylidyne(carbaborane) Complexes of the Group 6 Metals. Part 2. Alkylidene Group Capture on Protonation in the Presence of Chelating Phosphines

DOI: 10.1039/DT9920000401

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 401 - 408 (1992)

Update date:2022-08-06

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Authors:

Brew, Stephen A.Brew, Stephen A.

Jenkins, Paul D.Jenkins, Paul D.

Jeffery, John C.Jeffery, John C.

Stone, F. Gordon A.Stone, F. Gordon A.

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Article abstract of DOI:10.1039/DT9920000401

In CH2Cl2 solutions at ca. -78 deg C the salts 5-C2B9H9R'2)> (R'= Me or H) upon treatment with HBF4*Et2O, in the presence of dppm (Ph2PCH2PPh2) or dppe (Ph2PCH2CH2PPh2), afford the complexes (CO)2(η5-C2B9H9R'2)> (n = 1 or 2, R' = Me; n = 2, R' = H).The compound (CO)2(η5-C2B9H11)> was similarly prepared from 5-C2B9H11)>, dppe and HBF4*Et2O.In contrast, treatment of 5-C2B9H9Me2)> in CH2Cl2 at -78 deg C with HBF4*Et2O and dppe or dmpe (Me2PCH2CH2PMe2) gives the complexes 5-C2B9H8(Et)Me2>> (L2 = dppe or dmpe).The molecular structure of (CO)2(η5-C2B9H9Me2)> has been established by a single-crystal X-ray diffraction study.Within the five-membered WCPCP ring the bond distances are W-C 2.342(9), C-P 1.802(9), P-C 1.81(1) and P-W 2.482(3) Angstroem.The ligated carbon and phosphorus atoms of the ring, and the two essentially linearly bound CO ligands, form a pyramidal arrangement with the tungsten atom, the other side of which is co-ordinated by the nido-icosahedral C2B9H9Me2 cage in the usual η5 manner.The NMR spectra (1H, 13C-<1H>, 31P-<1H> and 11B-<1H>) of the new compounds are reported and discussed in relation to their structures.

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