Synthesis of new chiral ligands and their group VI metal alkylidene complexes

The new chelating chiral diol ligands (1S,2S)- and (1R,2R)-1,2-bis(2-hydroxy-2,2-bis-(trifluoromethyl)ethyl) cyclopentane (TBEC-H-2;1) were synthesized. The dilithium alkoxide of TBEC was reacted with Mo(CHCMe(2)Ph)(NAr)(OTf)(2)dme (2; Ar = 2,6-(i-Pr)(2)C6H3) to give the chiral alkylidene complex Mo(CHCMe(2)Ph)(NAr)(TBEC) (3). The ligand also reacts with W(eta(2)-diphenylcyclopropene)Cl-2(O)[P(OMe)(3)](2) (4), W(CHCHCOCH2CH2CH2O)(O)Cl-2[P(OMe)(3)] (5), and W(CHCHCPH2)(NAr)Cl-2[P(OMe)(3)](2) (6; Ar = 2,6-(i-Pr)(2)C6H3) to the give stable corresponding tungsten oxo vinylalkylidene complexes and tungsten amide vinylalkylidene complexes, respectively. These group IV alkylidene complexes show excellent catalytic activity in both ring-opening metathesis polymerization and in ring-closing metathesis processes.