Chromatography of organometallic and organometalloidal derivatives of amino alcohols : I. Retention indices of silatranes

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Abstract

The applicability of gas chromatography for the resolution of silatranes at 200–250° has been demonstrated. Retention indices were measured for 48 compounds of this class. Remarkably high values of the retention indices (I) and ΔI were found to be characteristic of all of the substances studied, which could not be accounted for on the basis of formal analysis of structural fragments. The relationship between the observed retention characteristics and silatrane structure was examined. A correlation was established between the retention characteristics and the properties of substituents attached to the silicon atom, permitting the assessment of dipole moments and induction constants. It was found that the extremely strong interaction of silatrane molecules with the stationary phase was due to the influence exerted by the transannular N → Si bond. The mean contribution of the structural fragment

to I was 430, 640 and 900 units on Apiezon L, OV-17 and OV-225, respectively. The separation of diastereomeric C-substituted silatranes was demonstrated and the order of elution is discussed. The character of changes in retention caused by the introduction of methyl groups in the α-position with respect to oxygen atoms indicates that the high I values are due mainly to the interaction of oxygen atoms with the acceptor groups of the stationary phase.

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