Formation of tungsten ethylidene complexes from diethyl complexes through a proton-catalyzed rearrangement of ethylene
Here, W(NAr) 2 Et 2 (Ar = 2,6-diisopropylphenyl) reacts with two equivalents of R F9 OH (OR F9 = OC(CF 3 ) 3 ) to yield W(NAr)(ArNH 2 )(OR F9 )2(C 2 H 4 ) complexes and ethane. In solution W(NAr)(ArNH 2 )(OR F9 ) 2 (C 2 H 4 ) decomposes to give R F9 OH, ethane, W(NAr)(OR F9 ) 2 (C 2 H 4 ), and W(NAr)(NHAr′)(ArNH 2 )(OR F9 ), in which Ar′ contains a dehydrogenated isopropyl group (Ar′ = (2-i-Pr)(6-CMe=CH 2 )C 6 H 3 ) coordinated to the metal. On a similar time scale W(NAr)(OR F9 ) 2 (CHCH 3 ) complexes are formed from W(NAr)(OR F9 ) 2 (C 2 H 4 ) through an ArNH 2 -catalyzed rearrangement of the ethylene ligand. W(NAr)(NHAr′)(ArNH 2 )(OR F9 ) reacts with cyclohexene to form methylenecyclohexene and complexes that contain an NHAr″ ligand where Ar″ is a disubstituted (methyl/aryl) alkylidene, (2-i-Pr)(6-CMe)C 6 H 3 ) that is tethered to the metal through the amido nitrogen. In contrast to W(NAr)(ArNH 2 )(OR F9 ) 2 (C 2 H 4 ), analogous OR F6 (OCMe(CF 3 ) 2 ) and OR F3 (OCMe 2 (CF 3 )) complexes are relatively stable at 22 °C.