95345-79-2Relevant academic research and scientific papers
Nucleophilic addition to coordinated cycloheptatriene: A mechanistic and structural study
Honig, Ephraim D.,Meng, Quin-Jin,Robinson, Ward T.,Williard, Paul G.,Sweigart, Dwight A.
, p. 871 - 877 (2008/10/08)
The addition of phosphorus and nitrogen donor nucleohiles (Nu) to the cycloheptatriene ring in (C7H8)Mn(CO)2L+ (1; L = CO, PPh3) yields (exo-NuC7H8)Mn(CO)2L+. N,N-Dimethylaniline undergoes an electrophilic aromatic substitution reaction with 1 (L = CO) to give (exo-Me2NC6H4C7H 8)Mn(CO)3, in which the carbon para to the NMe2 substituent is bonded to the C7H8 ring. Kinetic studies of the addition reactions show that 1 (L = CO) is an extremely reactive electrophile and that the relative nucleophilic reactivities are the same as found for other, less reactive, organometallic substrates as well as for free carbonium ions. A single-crystal X-ray analysis of [(exo-PPh3C7H8)Mn(CO)3]BF 4 showed that it crystallizes in the monoclinic space group P21/c with a = 9.595 (3) ?, b = 14.580 (4) ?, c = 19.574 (6) ?, β = 107.23 (8)°, and Rw = 0.0448. The structure shows that the dienyl carbons (C4-C5-C6-C7-C8) are planar and form a dihedral angle of 45.8° with the nonbonded plane (C10-C9-C8-C4). The carbon skeleton defining the cycloheptadienyl ring possesses approximate C8 symmetry.
