A series of neutral organosilicon compounds, R3Si(OPO) [R = Me (1), Et (2), Ph (3)], cis-R2Si(OPO)2 [R = Me (4), Et (5), iPr (6), tBu (7), Ph (9)], (CH2)3Si(OPO)2 (8), and cis-R2Si(OPO)Cl [R = Me (10), Et (11)] (OPO = 1-oxo-2-pyridinone) have been prepared and fully characterized. X-ray crystallographic analyses show 1 to be tetracoordinate, 3, 7, and 10 to be pentacoordinate, and 4, 5, 6, 8, and 9 to be hexacoordinate. In the hexacoordinate structures, a mixture of diastereomers is observed in the form of C/N site disorder in each OPO ligand. Variable-temperature 13C and 29Si NMR studies indicate reversible Si←OC bond dissociation occurring in all pentacoordinate and hexacoordinate complexes to a varying degree with greater tendency toward dissociation in hydrogen-bonding donor solvents. Significant weakening of the dative Si←OC bond in 3 is observed in the co-crystallized adduct solvate, 3·Ph3SiOH·½C5H12, providing structural evidence for the decrease in coordination number of the OPO ligand by hydrogen-bonding donors. In the hexacoordinate complexes, increasing steric bulk of ancillary ligands also was found to promote dissociation. 1H and 13C VT-NMR studies of 4, 6, 8, and 9 indicate stereoisomerization equilibria concurrent with Si←OC bond dissociation proposed to occur through trigonal bipyramidal intermediates. 1
Kraft, Bradley M. and Brennessel, William W. (2014). "Chelation and Stereodynamic Equilibria in Neutral Hypercoordinate Organosilicon Complexes of 1-Hydroxy-2-pyridinone." Organometallics 33.1, 157-171.
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