PUB - Publikationen an der Universität Bielefeld

(C2F5)2PNEt2 represents an excellent starting material for the selective synthesis of bis(pentafluoroethyl)phosphane derivatives. The moderately air-sensitive aminophosphane is accessible on a multi-gram scale by treating Cl2PNEt2 with C2F5Li. Treatment with gaseous HCl or HBr yielded the corresponding phosphane halides (C2F5)2PCl and the so far unknown (C2F5)2PBr in good yields. The hitherto unknown (C2F5)2PF was obtained by treating (C2F5)2PBr with excess antimony trifluoride. Treatment of (C2F5)2PCl with Bu3SnH led to the quantitative formation of (C2F5)2PH. Deprotonation formally yielded the (C2F5)2P- anion in a form that was stabilized by coordination to mercury ions to form the complex [Hg{P(C2F5)2}2(dppe)]. An improved high-yielding synthesis of (C2F5)2POH was achieved by treating (C2F5)2PNEt2 with p-toluenesulfonic acid. The gas-phase structures of (C2F5)2PH and (C2F5)2POH were determined by electron diffraction. The vibrational corrections employed in the data analysis of the diffraction data were derived from molecular dynamics calculations. Both compounds exist in the gas phase mostly as C1-symmetric cis,cis conformers with regard the orientation of the C2F5 groups relative to the functional groups H and OH. The presence of a second conformer at ambient temperature is likely in both cases. The refined amounts of dominant conformers are 94(6) and 85(6)% for (C2F5)2PH and (C2F5)2POH, respectively. The conformational behaviour was further explored by potential energy surface scans based on DFT calculations. Important experimental structural parameters for the most stable conformers are re(P-C)average = 1.884(3) angstrom for (C2F5)2PH and re(P-C)average = 1.894(4) angstrom and re(P-O) = 1.582(3) angstrom for (C2F5)2POH. The different coordination properties of (C2F5)3P, (C2F5)2POH, (CF3)3P and (CF3)2POH were evaluated by complex formation with [Ni(CO)4]: the maximum achievable number of CO ligands substituted by (C2F5)3P is 1, by (C2F5)2POH is 2, by (CF3)3P is 3 and by the smallest ligand (CF3)2POH is 4.