K. Mcneill et al., C-C AND C-H BOND ACTIVATION AT RUTHENIUM(II) - THE STEPWISE DEGRADATION OF A NEOPENTYL LIGAND TO A TRIMETHYLENEMETHANE LIGAND, Journal of the American Chemical Society, 119(46), 1997, pp. 11244-11254
Ruthenacyclobutane complexes (SiP3)(PMe3)Ru(CH2EMe2CH2) (SiP3 = MeSi(C
H2PMe2)(3); 1, E = C; 2, E = Si) were synthesized from (SiP3)(PMe3)RuC
l2 (3) and 2 equiv of the Grignard reagents, Me3ECH2MgCl. Metallacycle
1 was found to reversibly interconvert with the allyl complex (SiP3)R
u(Me)(eta(3)-CH2CMeCH2) (4) and PMe3 when heated above 75 degrees C. F
rom the results of kinetic studies and thermolysis of labeled material
, the interconversion is proposed to take place by reversible beta-met
hyl elimination/insertion. Conversion of 1 to 4 is an endothermic proc
ess (Delta H degrees = 14.3 +/- 1.1 kcal mol(-1)), but it is entropica
lly favorable (Delta S degrees = 40.9 +/- 2.8 cal K-1 mol(-1)) due to
the loss of the PMe3 ligand. Activation parameters for the beta-insert
ion were determined to be Delta H-double dagger = 26.0 +/- 1.2 kcal mo
l(-1) and Delta S double dagger = -10.5 +/- 0.9 cal K-1 mol(-1) Allyl
complex 4 has been isolated as a mixture of isomers (7:1 endo:exo). Th
e mechanism of interconversion of 4(endo) and 4(exo) was determined by
H-1{P-31} NMR spectroscopy (EXSY) to be a process involving a stereoc
hemically rigid, square-pyramidal eta(1)-intermediate. Thermolysis of
4 leads to loss of CH4 and the production of the trimethylenemethane c
omplex (SiP3)Ru(eta(4)-C(CH2)(3)) (7). The solid state structures of 1
and 7 were determined by X-ray diffraction.