Stabilizing the [RSn(μ<sub>2</sub>‑O)SnR]
Motif through Intramolecular N→Sn Coordination. Synthesis and
Characterization of [(RSn)<sub>2</sub>(μ<sub>2</sub>‑O)(μ<sub>2</sub>‑FcCOO)<sub>2</sub>(η-FcCOO)<sub>2</sub>]·THF
and {(RSn)<sub>2</sub>(μ<sub>2</sub>‑O)[(<i>t-</i>BuO)<sub>2</sub>PO<sub>2</sub>]<sub>2</sub>Cl<sub>2</sub>}·THF·2H<sub>2</sub>O (R = 2‑(Phenylazo)phenyl)
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Abstract
The reactions of RSnCl<sub>3</sub> (<b>1</b>; R = 2-(phenylazo)phenyl)
with FcCOOH or di-<i>tert</i>-butyl phosphate in refluxing
THF afforded the monoorganodistannoxanes [(RSn)<sub>2</sub>(μ<sub>2</sub>-O)(μ<sub>2</sub>-FcCOO)<sub>2</sub>(η-FcCOO)<sub>2</sub>]·THF (<b>2</b>) and {(RSn)<sub>2</sub>(μ<sub>2</sub>-O)[(<i>t-</i>BuO)<sub>2</sub>PO<sub>2</sub>]<sub>2</sub>Cl<sub>2</sub>}·THF·2H<sub>2</sub>O (<b>3</b>). The molecular structure of <b>2</b> contains seven-coordinate
tin centers in a distorted-pentagonal-bipyramidal geometry, while <b>3</b> contains six-coordinate tin centers in a distorted-octahedral
geometry. In the dinuclear compounds <b>2</b> and <b>3</b> the two tin centers are bridged by a μ<sub>2</sub>-O unit,
affording a rare Sn–O–Sn motif among monoorganostannoxanes.
In addition, each tin is also intramolecularly coordinated to the
nitrogen atom of the 2-phenylazophenyl substituent (N→Sn).
Further, in <b>2</b>, the two tin centers are bridged by two
isobidentate ferrocenecarboxylate ligands; each tin center also is
bound to a chelating ferrocenecarboxylate ligand. On the other hand,
in <b>3</b>, while the two tin centers are bridged by two isobidentate
di-<i>tert</i>-butyl phosphate ligands, each tin center
also has a terminal chloride ligand
