A surprising reaction of trimethylphosphine with the unsaturated diruthenium complex [(?6-C6Me6)2Ru2(?2-H)3]+: synthesis and molecular structure of the cations [(?6-C6Me6)Ru2(PMe3)3(?2-H)3]+ and [(?6-C6Me6)2Ru2(PMe3)2(?2-H)(H)2]+
Author(s)
Tschan, Mathieu J. L.
Cherioux, Frederic
Date issued
2007
In
Eur. J. Inorg. Chem.
Vol
4
From page
509
To page
513
Subjects
trimethylphosphine reaction unsatd diruthenium hydride fluoroborate complex crystal mol structure hydride bridged hexamethylbenzene ruthenium trimethylphosphine unsatd
Abstract
Whereas arom. or aliph. phosphines undergo cleavage of the P-C bond in the reaction with [(?6-C6Me6)2Ru2(?2-H)3]+ to give phosphido-bridged diruthenium cations of the type [(?6-C6Me6)2Ru2(?2-PR2)(?2-H)2]+, trimethylphosphine surprisingly yields the substitution product [(?6-C6Me6)Ru2(PMe3)3(?2-H)3]+ (1), as well as the racemic intermediate [(?6-C6Me6)2Ru2(PMe3)2 (?2-H)(H)2]+ (2), in the form of the tetrafluoroborate salts. In complex 2, the hydrido ligands are fluxional in soln., as shown by variable-temp. 1H NMR spectroscopy. Cation 1 reacts with p-bromothiophenol to give the complex [(?6-C6Me6)2Ru2(PMe3)3{?2-(p-Br-C6H4)-S}(?2-H)2]+ (3), isolated as the tetrafluoroborate salt. [on SciFinder(R)]
Publication type
journal article