Reactions of [RuH( η3C 3H 5)(CO)(P iPr 3) 2] and [Ru( η2C 2Ph 2)(CO)(P iPr 3) 2] with terminal alkynes: synthesis and characterization of new five- and six-coordinate bis(alkynyl) and alkynyl(vinyl) derivatives of ruthenium(II)

Abstract

The reaction of the complex [RuHCl(CO)(P iPr 3) 2] with C 3H 5MgBr affords [RuH( η 3C 3H 5)(CO) (P iPr 3) 2] ( 2). This complex reacts with terminal alkynes. With CyC 2 it yields [Ru(C 2Cy) 2(CO)(P iPr 3) 2] ( 3), whereas with Me 3SiC 2H it gives a mixture of [Ru(C 2SiMe 3) 2(CO)(P iPr 3) 2] ( 4) and [ Ru(C 2SiMe 3) {(E)- CH=CHSiMe 3}( CO)( P iPr 3) 2]( 5) . 4 was obtained as a spectroscopically pure oil by reaction of [RuH( η 2H 2BH 2)(CO)(P iPr 3) 2] ( 15) with Me 3SiC 2H. 2 also reacts with PhC 2Ph giving [Ru( η 2C 2Ph 2)(CO)(P iPr 3) 2] ( 6), which with RC 2H then yields [ Ru(C 2R ){(E)- CH=CHR}( CO)( P iPr 3) 2] ( R = Cy ( 11), or −CO 2CH 3 ( 12)) . Under CO, 3 and 4 give [Ru(C 2R) 2(CO) 2(P iPr 3) 2] ( R = Cy ( 7) or ( Me 3Si ( 8)), but 5, 11 and 12 afford [ Ru(C 2R ){(E)- CH=CHR}( CO) 2( P iPr 3) 2] ( R = Me 3Si ( 9), Cy ( 13), or − CO 2CH 3 ( 14)) . 15 catalyzes the cyclotrimerization of methyl propiolate to give a mixture of 1,3,5-C 6H 3(CO 2CH 3) 3 and 1,2,4-C 6H 3(CO 2CH 3) 3 in a 2:1 molar ratio.