Dichloromethane Alkylates a Trithiolato-Ruthenium Complex to Yield a Methylene-Bridged Thioether Core. Synthesis and Structural Comparison to the Thiolato-Ruthenium Precursor

The previously reported triphosphino/trithiolato-ruthenium anion,
[tris-(2-diphenylphosphinothia-phenolato)ruthenium(II)]-, [Ru(DPPBT)3]-, has been isolated as the PPN salt (PPN = bis(triphenylphosphoranylidene) ammonium), 1, from chlorobenzene/ether as
light-orange crystalline plates, and the X-ray crystal structure has
been determined. In dichloromethane, the cis positioned thiolates
are alkylated by solvent yielding the methylene-bridged triphosphino/dithioether/thiolato complex [(bis-(2-diphenylphosphinothiaphenolato)methane)(2-diphenyl-phosphinothiaphenolato)ruthenium(II)]chloride, [Ru((DPPBT)2CH2)(DPPBT)]Cl (2). Dichloromethane
solutions of 1 layered with hexanes yield 2 as orange cubes. The
ruthenium−sulfur bond distances in the alkylated, thioether product
are slightly shorter than in the thiolate precursor. Within 2, the
iron−thioether bond distances are comparable to the iron−thiolate
distances.