Abstract
A phosphino-oxazine based ligand (L; 2-(2-(diphenylphosphino)phenyl)-2,4-dihydro-1H-benzo[d][1,3]oxazine) showing a temperature-dependent equilibrium between a closed bidentate (L-PN) and an opened tridentate (L-PNO) form, has been synthesized and its coordination behavior toward ruthenium(II) centers studied. Under different experimental conditions, two different species bearing the ligand in either its bidentate or tridentate coordination mode were isolated by reaction with Ru(PPh3)(3)Cl-2. These species, respectively formulated as [Ru(PPh3)(L-PNO)Cl-2] (1) and [Ru(PPh3)(L-PN)Cl-2] (2), were fully characterized via NMR in solution and by an X-ray structural determination. Notably, compound 2 reacts with an excess of ethyl diazoacetate (EDA) in CH2Cl2 to give a stable eta(3)-diethyl maleate complex, [Ru(L-PN)(cis-EtO(O)CCH=CHC(O)OEt)Cl-2] (3). The crystal structure of 3 has also been determined. Substitution reactions with 4-picoline (4-Me-py) performed on 1 led to two new complexes: the neutral complex [Ru(4-Me-py)(L-PNO)Cl-2] (5) and the salt [Ru(4-Me-py)(2)(L-PNO)Cl](Cl) (6a). The latter compound catalyzed the intermolecular cyclopropanation of styrene with EDA in high yields and with elevated cis diastereoselectivity (i.e., cis/trans = 80/20).