The isopropyl chloro complex Tp(Me2)NbCl(i-Pr)(PhC&tbd1;CMe) (2) [Tp(Me2) = hydrotris(3,5-dimethylpyrazolyl)borate] exhibits a beta-agostic structure in the crystal. The conformation of the alkyl group is such that the agostic methyl group lies in the Calpha-Nb-Cl plane and the nonagostic one, in a wedge formed by two pyrazole rings. As observed by solution NMR spectroscopy, restricted rotation about the Nb-C bond allows the observation of an equilibrium between this species, 2beta, and a minor alpha-agostic rotamer 2alpha. A putative third rotamer which would have the secondary hydrogen in the wedge is not observed. Similar behavior is observed for related Tp'NbCl(i-Pr)(R(2)C=CMe) [Tp' = Tp(Me2), R(2) = Me (3); Tp' = Tp(Me2,4Cl), R(2) = Ph (4)]. The two diastereomers of the sec-butyl complex Tp(Me2)NbCl(sec-Bu)(MeC=CMe) (5) have been separated. In the crystal, 5CR-AS has a beta-agostic methyl group with the ethyl group located in the wedge formed by two pyrazole rings. The same single beta-agostic species is observed in solution. The other diastereomer, 5AR-CS has a beta-agostic methylene group in the solid state, and the methyl group sits in the wedge. In solution, an equilibrium between this beta-agostic methylene complex 5AR-CSbeta and a minor alpha-agostic species 5AR-CSalpha, where the ethyl substituent of the sec-Bu group is located in the wedge between two pyrazole rings, is observed. NMR techniques have provided thermodynamic parameters for these equilibria (K = 2beta/2alpha = 4.0 +/- 0.1 at 193 K, DeltaG(o)(193) = -2.2 +/- 0.1, DeltaH(o) = -7.4 +/- 0.1 kJ mol(-)(1), and DeltaS(o) = -27 +/- 1 J K(-)(1) mol(-)(1)), as well as kinetic parameters for the rotation about the Nb-C bond (at 193 K, DeltaG(2)= 47.5 +/- 2.5, DeltaH= 58.8 +/- 2.5 kJ mol(-)(1), and DeltaS = 59.0 +/- 10 J K(-)(1) mol(-)(1)). Upon selective deuteration of the beta-methyl protons in Tp(Me2)NbCl[CH(CD(3))(2)](PhC=CMe) (2-d(6)), an expected isotope effect that displaces the equilibrium toward the alpha-agostic rotamer is observed (K = 2-d(6)beta/2-d(6)alpha = 3.1 +/- 0.1 at 193 K, DeltaG(o)(193) = -1.8 +/- 0.1, DeltaH(o) = -8.3 +/- 0.4 kJ mol(-)(1) and DeltaS(o)= -34 +/- 2 J K(-)(1) mol(-)(1)). The anomalous values for DeltaH(o) and DeltaS(o) are discussed. Hybrid quantum mechanics/molecular mechanics calculations (IMOMM (B3LYP:MM3)) on the realistic model Tp(Me2)NbCl(i-Pr)(HC=CMe) have reproduced the energy differences between the alpha- and beta-agostic species with remarkable accuracy. Similar calculations show that Tp(Me2)NbCl(CH(2)Me)(HC=CMe) is alpha-agostic only and that Tp(5)(-)(Me)NbCl(CH(2)Me)(HC=CMe), which has no methyl groups at the 3-positions of the pyrazole rings, is beta-agostic only. Analysis and discussion of the computational and experimental data indicate that the unique behavior observed for the secondary alkyl complexes stems from competition between electronic effects favoring a beta-agostic structure and steric effects directing a bulky substituent in the wedge between two pyrazole rings of Tp(Me2). All of the se...

H 11 (4),) have been prepared from Tp Me2 NbCl 2 (MeC᎐ ᎐ ᎐ CMe). The cyclopropyl complex 2a shows no sign of C-H agostic interactions either in the solid state (X-ray) or in solution. In contrast, the NMR spectra of 3 and 4 are temperature dependent as a consequence of an equilibrium between a major α-agostic species and a minor non-agostic one. Hybrid QM/MM calculations are used to rationalise the behaviour of these cycloalkyl species, and illustrate the subtle interplay of steric and electronic effects in these systems.