Five-Membered Ruthenacycles: Ligand-Assisted Alkyne Insertion into 1,3-N,S-Chelated Ruthenium Borate Species

Building upon previous work, the chemistry of [(η⁶ -p-cymene)Ru{P(OMe)₂ OR}Cl₂ ], (R=H or Me) has been extended with [H₂ B(mbz)₂ ]^- (mbz=2-mercaptobenzothiazolyl) using different Ru precursors and borate ligands. As a result, a series of 1,3-N,S-chelated ruthenium borate complexes, for example, [(κ² -N,S-L)PR₃ Ru{κ³ -H,S,S'-H₂ B(L)₂ }], (2 a-d and 2 a'-d'; R=Ph, Cy, OMe or OPh and L=C₅ H₄ NS or C₇ H₄ NS₂ ) and [Ru{κ³ -H,S,S'-H₂ B(L)₂ }₂ ], (3: L=C₅ H₄ NS, 3': L=C₇ H₄ NS₂ ) were isolated upon treatment of [(η⁶ -p-cymene)RuCl₂ PR₃ ], 1 a-d (R=Ph, Cy, OMe or OPh) with [H₂ B(mp)₂ ]^- or [H₂ B(mbz)₂ ]^- ligands (mp=2-mercaptopyridyl). All the Ru borate complexes, 2 a-d and 2 a'-d' are stabilized by phosphine/phosphite and hemilabile N,S-chelating ligands. Treatment of these Ru borate species, 2 a'-c' with various terminal alkynes yielded two different types of five-membered ruthenacycle species, namely [PR₃ {C₇ H₄ S₂ -(E)-N-C=CH(R')}Ru{κ³ -H,S,S'-H₂ B(L)₂ }], (4-4'; R=Ph and R'=CO₂ Me or C₆ H₄ NO₂ ; L=C₇ H₄ NS₂ ) and [PR₃ {C₇ H₄ NS-(E)-S-C=CH(R')}Ru{κ³ -H,S,S'-H₂ B(L)₂ }], (5-5', 6 and 7; R=Ph, Cy or OMe and R'=CO₂ Me or C₆ H₄ NO₂ ; L=C₇ H₄ NS₂ ). All these five-membered ruthenacycle species contain an exocyclic C=C moiety, presumably formed by the insertion of a terminal alkyne into the Ru-N and Ru-S bonds. The new species have been characterized spectroscopically and the structures were further confirmed by single-crystal X-ray diffraction analysis. Theoretical studies and chemical-bonding analyses established that charge transfer occurs from phosphorus to ruthenium center following the trend PCy₃ 3 3 3 .