Synthesis and structural characterization of organotin(IV) complexes with ferrocenyldithiophosphonate ligands

• New organometallic tin dithiophosphonates with bulky ligands.
• There are very few organotin dithiophosphonates structurally characterized.
• The presence of bulky ligands precludes the intermolecular interactions.

The reaction of ammonium salts of benzylferrocenyldithiophosphonate ligands [NH4][S2P(OR)(Fc)] [R = Bz (1), 4-(iPr)-Bz (2), 4-(tBu)-Bz (3), 4-(Ph)-Bz (4), 3-(OBz)-Bz (5); Bz = benzyl, Fc = ferrocenyl] with organotin(IV) chlorides Ph2SnCl2, nBu2SnCl2 and Ph3SnCl, gave the corresponding organotin(IV) benzylferrocenyldithiophosphonates [Ph2Sn{S2P(OR)(Fc)}2] [R = Bz (6), 4-(iPr)-Bz (7), 4-(tBu)-Bz (8), 4-(Ph)-Bz (9), 3-(OBz)-Bz (10)], [nBu2Sn{S2P(OR)(Fc)}2] [R = Bz (11), 4-(Ph)-Bz (12)] and [Ph3Sn{S2P(OBz)(Fc)}] (13). Compounds 6–13 were characterized by elemental analyses, infrared, 1H, 13C{1H},31P{1H} and 119Sn{1H}NMR spectroscopy and ESI mass spectrometry, while complexes 6, 11 and 13 were also characterized by single-crystal X-ray diffraction studies. The dithiophosphonate ligands display an anisobidentate coordination mode upon interaction with the metal center. The solid-state structures of the disubstituted complexes 6 and 11 exhibit a trans arrangement for the ferrocenyl groups from the dithiophosphonate ligands.

The reaction of ammonium salts of benzylferrocenyldithiophosphonate ligands with organotin chlorides lead to organotin(IV) benzylferrocenyldithiophosphonates [R2Sn{S2P(OR′)(Fc)}2]. These compounds exhibit an anisobidentate coordination mode upon interaction with the metal center. The solid-state structures of the disubstituted complexes exhibit a trans arrangement for the ferrocenyl groups from the dithiophosphonate ligands.Figure optionsDownload as PowerPoint slide