Three-coordinate RhX[P(C6H11)3]2, their reactions with N2 and O2, and the trans-influence in RhX[P(C6H11)3]2L (X = anionic,L = neutral ligand) |
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| Authors: | H.L.M. van Gaal F.L.A. van den Bekerom |
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| Affiliation: | Department of Inorganic Chemistry, Catholic University, Toernooiveld, Nijmegen The Netherlands |
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| Abstract: | Three-coordinate RhX(PCy3)2 complexes (X = F, Cl, Br, I; Cy = cyclohexyl) have been prepared from rhodium(I) cyclooctene compounds. RhCl(PCy3)2 is in equilibrium with its dimer. The complexes RhX(PCy3)2 (X = Cl, Br, I) form the adducts RhX(PCy3)2(N2) with dinitrogen, the times for N2-fixation being 4 days, 3 hours and 15 minutes respectively. The three-coordinate complexes form four-coordinate dioxygen adducts RhX(PCy3)2(O2) which have unusually high ν(OO) at about 990 cm?1. This high frequency is attributed to the four-coordination, which is exceptional for dioxygen complexes. From RhF(PCy3)2 carbonyl, ethene, and diphenylacetylene complexes RhX(PCy3)2L (X = F, Cl, Br, I, N3, NCO, NCS; L = CO, C2H4, C2Ph2) (X = CN, NO3, acetate; L = CO) have been prepared. The trans-influence of the anionic ligands on the infrared frequencies of the neutral ligands is discussed in terms of the different π-bonding properties of the X- and L-ligands. |
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| Keywords: | To whom correspondence should be addressed. |
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