A series of paramagnetic (S = 3/2) chromium half-sandwiches of the type CpCrX2D (D = donor) were synthesized by starting from [CpCrX2]2, Cp2Cr, CpCrCl2(THF), and Cp*Cr(CH3)2[P(CH3)3]. Besides the parent cyclopentadienyl (Cp) the alkylated derivatives CH3C5H4, (CH3)5C5 (Cp*), and C2H5(CH3)4C5 were bound to chromium. The electronegative substituent was X = F, Cl, Br, I, and triflate, while the donors were three ethers, four ketones, dimethylsulfoxide, acetonitrile, methylisocyanide, pyridine, and seven molecules ER3 where E = N, P, As, Sb. The half-sandwiches were partly isolated and partly established in solution. The 13C and 1H NMR spectra showed strongly shifted signals which allowed to quantitatively investigate the equilibrium between CpCrX2D and the anti ferromagnetic species [CpCrX2]2. The NMR signals of CpCrX2D and its substituted derivatives appeared in characteristic ranges thus providing a means of rapid identification. Considerable spin density was found to be induced on the ligands; it is negative in the Cp π system. As for the donors, inter- and intramolecular dynamic behavior as well as selective spin transfer to the γ protons of acetonitrile, methylisocyanide, and ketones was detected.
The Intramolecular Dynamic Behavior of Tetraaryl Allyl Radicals