TRANSITION-METAL COMPLEXES WITH SULFUR LI GANDS .115. PROTONATION ANDALKYLATION OF THIOLATE DONORS IN RU(II) COMPLEXES WITH [RU(S-'BU(5)')] FRAGMENTS -MERCAPTO-3,5-DI-T-BUTYLPHENYLTHIO)DIETHYLSULFIDE)

Reaction of meso-[Ru(L)('S-bu(5)')] complexes (L = CO (1), PPh(3), PCy (3)) with one equivalent of oxonium salts R(3)OBF(4) (R = CH3, C2H5) y ields the C-I symmetrical monoalkyl derivatives [Ru(L)('S-bu(5)'-R)]BF 4 (L = CO, R = CH3 (2), C2H5 (3); L = PPh(3), R = CH3 (5), L = PCy(3), R = CH3 (6)), in which one of the thiolate donors of the starting com plexes is alkylated diastereospecifically. Monoalkylation of the binuc lear complex [Ru('S-bu(5)')](2) leads to C-i symmetrical [Ru('S-bu(5)' -CH3)](2)(BF4)(2) (7) which gives the hydrazine complex [mu-N2H4{Ru('S -bu(5)'-CH3)}(2)](BF4)(2) . N2H4 (9) upon reaction with N2H4. Reaction of 1 with 1.5 equivalents of CF3SO3H yields the isolable thiol comple x [Ru(CO)('buS(5)'-H)]CF3SO3 . 0.5 CF3SO3H (4). The H-1-NMR spectra ar e temperature-dependent and indicate exchange of the thiol proton betw een the thiolate conors of the 'S-bu(5)'(2-) ligand. Twofold protonati on of 1 could only be proved IR-spectroscopically, dialkylation of 1, however, yields isolable [Ru(CO)('S-bu(5)'-(CH3)(2))](BF4)(2) (8) as a mixture of diastereomers. The IR stretching frequencies nu(CO) of the CO complexes indicate that the electron densities at the ruthenium ce nters are decreased and the Ru-L bonds are weakened. However, the liga nds L in the [Ru(L)('S-bu(5)'-R)]BF4 complexes do not exchange more re adily than in the parent complexes.