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Carbene Complexes. Part 18. Synthetic Routes to Electron-rich Olefin-derived Monocarbenerhodium(I) Neutral and Cationic Complexes and their Chemical and Physical Properties

DOI: 10.1039/DT9840002355

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2355 - 2364 (1984)

Update date:2022-08-16

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Authors:

Doyle, Michael J.Doyle, Michael J.

Lappert, Michael F.Lappert, Michael F.

Pye, Peter L.Pye, Peter L.

Terreros, PilarTerreros, Pilar

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Article abstract of DOI:10.1039/DT9840002355

Electron-rich olefins of general type <=<*>C(NR)CH2CH2<*>NR>2 (LR2; R=Me, Et, Ph, 4-MeC6H4. 4-MeOC6H4, or 2-MeOC6H4) undergo reaction with a variety of rhodium(I) precursors via ligand displacement or chloride-bridge cleavage to afford monocarbenerhodium(I) complexes, such as R)(PPh3)2>, R)>, or R)(PPh3)>>LR= =<*>C(NR)CH2CH2N<*>R, cod=cyclo-octa-1,5-diene>; complexes Me)(PPh3)X> Me= =<*>CN(Me)CH2CH2CH2N<*>Me, X= CO or PPh3> have similarly,been obtained from the olefin L'Me2.From these, further complexes may be obtained by ligand (neutral or anionic) exchange processes : trans-R(PPh3)2>, trans-R)(PPh3)2>X (X=Br, Cl, ClO4, or I), R)(PPh3)> (X=BH4 or ClO4), cis-R)> (X=Cl or NO3), R)> (X= CH2SiMe3, ClO4, or NO3), cis-R)(PPh3)>, and R)>.In many of the reactions some of these ligand displacements at RhI proceed without retention of stereochemistry and it is likely that the observed product is the thermodinamically preferred isomer.Other chemical properties of the monocarbenerhodium(I) complexes relate to (i) rare examples of the displacement of LR from Rh by PPh3 or Ph2PCH2CH2PPh2 under rather forcing conditions, and (ii) oxidative addition (not particularly facile) of HCl, Cl, or C2(CN)4.The 45 new complexes heva been characterised by analysis and spectroscopy (i.r. and 1H and 31P n.m.r.) and, where appropriate, relative molecular mass determination , and electrical conductivity.From J(31P-103Rh) coupling constants it is concluded that LR has a greater trans influence than PPh3 but a lower cis influence.

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Product name:Carbonylbis(triphenylphosphine)rhodium(I) chloride

Cas No:13938-94-8

13938-94-8

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