references cited therein. (13) Electron acceptors which are also conjugated with the alkene r system will polarize the HOMO in the same directions as, but to a smaller extent than, Inductive acceptors.8 (14) There has been a suggestion that Me is an acceptor relative to H when attached to an sp3 carbon [C. A. Grob, Angew. Chem. lnt. Ed. Engl., 15, 569 (1976), and references cited therein]. The product ratio discussed here reflect this, but the IP changes do not. A subtle role of solvent may be involved. (15) J. Bastideand J. P. Maier, Chem. Phys., 12, 144 (1976 Li+, CUR+), the e component of which greatly stabilizes the most symmetrical q5 coordination. The lower the energy of the e acceptor set and the better the overlap with its Cp counterpart, the more are q2 and q5 stabilized relative to 7'. In the case of XH3+ (X = C, Si, Ge, Sn) an e acceptor orbital moves to lower energy as one proceeds down the group, and this is responsible for the decreasing barrier for sigmatropic shifts in CpXH3. The XH2 case, which yields a number of interesting collapse structures, is analyzed in detail for X, a main group center. Contrast the interaction of a cyclopentadienide anion and a proton with the interaction of the same anion and a Mn(CO)3+ fragment. Both result in stable molecules: cyclopentadiene (1) and V~-C~M~( C O )~ (2). But what a difference in the equilibrium geometries of these end products of the interaction! If we focus our attention on the cyclopentadienide site where the interacting partner settles down, then the proton chooses a position near to one carbon of the ring, but the Mn(C0)3+ fragment sits directly over the center of the ring. The ramifications of this differential are the concern of this paper. We will examine the interaction of a cyclopentadienide (CsHs-, Cp) ion with an interacting group X, X = H+, CH3+, SiR3+, Mn(C0)3+, CH22f, CH2. The result will consist of some conclusions concerning the equilibrium geometry of CpX as well as the relative energetics of the various haptotropic reactions of this Consider the passage of the interacting group X across the face of a Cp molecule, moving as indicated in 3 in a plane parallel to the Cp ring. Let the distance d be a separation at which there is sizable interaction between the frontier orbitals of X and the Cp a system. For a surface so constrained the asymmetric unit that need be calculated consists of the shaded area in 4, and two of the three boundaries of that area are contained in a transit along a line shown in projection in 5. Mirror symmetry is maintained at all points. The numbers nq shown along that line are convenient labels invoking a connection to the inorganic 7" notation* for denoting an approximate coordination geometry. In order to avoid confusion with structure numbers and ring carbon numbers, we have labeled the various sites along the transit line as 17, 217, . . . , 57. The site labeled 17, or some geometry near it, corresponds to or simple u interaction, such as we have in the collapse product cyclopentadiene. The 7IS site 57 is where one better come up with maximum stabilization for X = Mn(C0)3+. The site labeled 27 positions X over the center of a bond, and obviously will describe the important transition state region for a sigmatropic shift of a system like cyclopentadiene. 37 and 47 are not so easily defined. Experimentally, slippage of Cp rings from q5 coordination is often observed and q3 or q4 coordination may or may not be invoked. Somewhat arbitrarily we define 317 at the intersection of the transit line with the line joining C-2 and C-5 projected on the transit plane. The tetrahapto coordination site is most ambiguous (it could be near 37 or near 57), and SO we will not label any position as such. The analysis will consist of an inspection of interaction diagrams for the orbitals of Cp and X, as the ligand X and its position along the transit are varied. The qualitative arguments based on symmetry and overlap are supported by extended Huckel calculations whose details are given in the Appendix. The reader should be aware that this is an approximate metho
