The addition of Ph2P(2-C6H4OH)
to [(η6-p-cymene)RuCl(μ-Cl)]2 led to the formation of three distinct products, depending
on the experimental conditions. The previously reported [(η6-p-cymene)RuCl{κ2
P,O-PPh2(2-C6H4O)}], 1, was obtained in 90% yield using MeOH
as the solvent, in the presence of a base (Et3N). Conversely,
[(η6-p-cymene)RuCl{κ2
P,O-PPh2(2-C6H4OH)}]Cl, [2]Cl, was afforded (88% yield)
in MeOH without using the base. However, [(η6-p-cymene)RuCl2{κP-PPh2(2-C6H4OH)}], 3, was the
major species in chlorinated solvents. Compounds 1, [2]Cl, and 3 were characterized by analytical
and spectroscopic (IR, NMR) methods. The X-ray structures of [2]+ and 3 were determined, with the
latter forming hydrogen bond dimeric units in the solid state. The
dissolution of [2]Cl into a series of deuterated solvents,
except methanol, led to rapid equilibration between [2]Cl and 3, revealing the hemilabile behavior of the
phosphino-phenol ligand. According to Pulsed-Field Gradient Spin Echo
(PGSE)-NMR and DFT studies, the dimeric nature of 3 persists
in solution; thus, the hydrogen-bonding properties of MeOH are crucial
to stabilize [2]Cl with respect to 3, with
the latter being 3.4 kcal mol–1 more stable than
the former in the gas phase. Compound 1 underwent electrophilic
additions by HCl, HBF4, and MeCOCl to give, respectively,
[2]Cl (the reverse process being viable with Et3N), [2]BF4, and the ester [(η6-p-cymene)RuCl2{κP-PPh2(2-C6H4OCOMe)}], 5. The reaction of 1 with AgNO3 afforded the
nitrate complex [(η6-p-cymene)Ru(NO3){κ2
P,O-PPh2(2-C6H4O)}], 4. Compounds [2]BF4, 4, and 5 were isolated in the solid state in good to high yields
and characterized by elemental analysis and IR and NMR spectroscopy.