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5692687 
Dissertation 
Structural, mechanistic and synthetic chemistry of actinacycles 
Smith, GM 
1987 
Evanston, IL 
Northwestern University 
Doctoral Dissertation 
English 
This thesis first reports on several features of intramolecular, and in one case intermolecular, C--H bond activation reactions which occur at thorium centers. The studies of intramolecular C--H bond activation include the syntheses, structures and cyclometalation reactions of a series of bis(pentamethylcyclopentadienyl)thorium dialkyl complexes. The mechanism for cyclometalation is proposed to involve a concerted, heterolytic process with hydrogen atom abstraction and metallacycle formation occurring in a four-center transition state. The equilibrium constant, as well as forward and reverse rate constants for the C--H bond activating equilibrium: Cp'(,2)Th(CH(,2)SiMe(,3))(,2) () Cp'(,2)ThCH(,2)SiMe(,2)CH(,2) + Me(,4)Si (Cp' = (eta)('5) - C(,5)Me(,5)); have been measured and give (DELTA)H('o) = +4.6(3) kcal mol('-1), and (DELTA)S('o) = +16.6(5) eu; (DELTA)H('(DBLDAG))(,fwd) = +22.4(3) kcal mol('-1) and (DELTA)S('(DBLDAG))(,fwd) = -17.6(5) eu; and (DELTA)H('(DBLDAG))(,rev) = +17.8(5) and (DELTA)S('(DBLDAG))(,rev) = -34.2(5) eu. Second, this thesis reports on the synthesis, structures, and dynamic NMR behavior of the methylene bridged heterobimetallic complexes obtained in reactions of Cp'(,2)Th(CH(,2)CMe(,2)CH(,2)) (1), as follows. Treat- ment of 1 with Cp(,2)ZrMe(,2) (Cp = (eta)('5)-C(,5)H(,5)) in saturated hydrocarbon solvents yields Cp'(,2)Th((mu)-CH(,2)) ((mu)-h1:(eta)('5)-C(,5)H(,4))ZrCp(Me) (2) and neo- pentane, while reaction between 1 and Cp(,2)HfMe(,2) gives Cp'(,2)Th((mu)- CH(,2)) ((mu)-h1:(eta)('5)-C(,5)H(,4))HfCp(Me) (3). Reaction of 1 and Cp''(,2)ZrMe(,2) gives Cp'(,2)Th((mu)-CH(,2)) ((mu)-h1:(eta)('5)-3,4-C(,5)Me(,2)H(,2))Zr(Cp'')Me (Cp'' = (eta)('5)-1,2-Me(,2)H(,3)C(,5)) (4). These compounds all exhibit a fluxional process which exchanges diastereotopic hydrogen atoms on the (mu)-methyl- ene with (DELTA)G('(DBLDAG)) (T(,c)) for 2 of 11.2(3) kcal mol('-1) (277 K) in toluene and 11.5(2) kcal mol('-1) (287 K) in THF, for 3 of 11.5(2) kcal mol('-1) (268 K) in toluene, and for 4 of 11.8 (2) kcal mol('-1) (282 K) in toluene. Finally, this thesis describes the synthesis and properties of the actinide s-cis-diene/cis-2-butene-1,4-diyl complexes Cp'(,2)U((eta)('5)-C(,4)H(,6)) (5), Cp'(,2)Th((eta)('4)-C(,4)H(,6)) (6), and Cp'(,2)Th((eta)('4)-CH(,2)C(Me)C(Me)CH(,2)) (7). These complexes may be prepared from Cp'(,2)MCl(,2) and the appropriate (THF)(,2)Mg(CH(,2)C(R)C(R)CH(,2)) reagent in THF.