Synthesis of New Half‐Sandwich Ruthenium( II ) Complexes Bearing Alkenyl‐ and Alkynylphosphane Ligands

Carbonyl substitution of the complex [RuI( 5 ‐C 9 H 7 )(CO) 2 ] with the activated phosphanes Ph 2 PR (R = CH 2 CH=CH 2 , CH 2 CH 2 CH=CH 2 , and C≡CPh) affords the complexes [RuI( 5 ‐C 9 H 7 )(CO)(Ph 2 PR‐ P )] [R = CH 2 CH=CH 2 ( 1a ), CH 2 CH 2 CH=CH 2 ( 1b ), C≡CPh ( 1c )]. The reaction of the complex [RuCl( 5 ‐C 9 H 7 )(PPh 3 ) 2 ] with the corresponding phosphanes, in refluxing THF, gives the complexes [RuCl( 5 ‐C 9 H 7 )(PPh 3 )(Ph 2 PR‐ P )] [R = CH 2 CH 2 CH=CH 2 ( 2b ), C≡CPh ( 2c )] by substitution of PPh 3 . The cationic derivatives [Ru( 5 ‐C 9 H 7 )(L)(Ph 2 PR‐ 3 P , C , C )][X] [L = CO, X = SbF 6 , R = CH 2 CH=CH 2 ( 3a ), CH 2 CH 2 CH=CH 2 ( 3b ); L = PPh 3 , X = PF 6 , R = CH 2 CH 2 CH=CH 2 ( 4b )] have been prepared by treatment of the complexes 1a , b and 2b with a halide abstractor such as AgSbF 6 or NaPF 6 , respectively. Deprotonation reactions of the complexes 3b and 4b with cesium carbonate have beencarried out, giving rise to the neutral complexes [Ru( 5 ‐C 9 H 7 )(L)(Ph 2 PCH 2 CH=CHCH 2 ‐ 2 P , C )] [L = CO ( 5a ), PPh 3 ( 5b )]. The reaction of complex 3a with MeCN generates the complex [Ru( 5 ‐C 9 H 7 )(MeCN)(CO)(Ph 2 PCH 2 CH=CH 2 ‐ P )][SbF 6 ] ( 6 ). The vinylidene [Ru( 5 ‐C 9 H 7 )(PPh 3 )(Ph 2 PC≡CPh‐ P ){C=C(Ph)H}][PF 6 ] ( 7 ) and allenylidene [Ru( 5 ‐C 9 H 7 )(PPh 3 )(Ph 2 PC≡CPh‐ P )(C=C=CPh 2 )][PF 6 ] ( 8 ) derivatives have been synthesized by reaction of complex 2c with phenylacetylene or 1,1‐diphenylprop‐2‐yn‐1‐ol, respectively. The structures of the derivatives 1c , 3a , and 4b have been determined bysingle‐crystal X‐ray diffraction analysis. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)