Synthesis and Characterization of [(η6-arene)RuCl2(R2AsCHCH2)] and Tethered Arsinopropylarene−Ruthenium(II) Complexes

The complexes [(η 6 -arene)RuCl 2 (R 2 AsCH CH 2 )] [arene = MeC 6 H 5, R = Ph ( 1a ), R = Cy ( 1b ); p -MeC 6 H 4 Me, R = Ph ( 2a ), R = Cy ( 2b ); o -MeC 6 H 4 Me, R = Ph ( 3a ), R = Cy ( 3b ); 1,3,5-Me 3 C 6 H 3, R = Ph ( 4a ); p -MeC 6 H 4 CHMe 2, R = Ph ( 5a ), R = Cy ( 5b ); 1,2,4,5-Me 4 C 6 H 2, R = Ph ( 6a ), R = Cy ( 6b ); C 6 Me 6, R = Ph ( 7a )] have been synthesized by reacting [(η 6 -arene)RuCl 2 ] 2 with the respective vinyl arsine. The compounds [(η 6 -MeC 6 H 5 )RuCl 2 (Ph 2 AsCH CH 2 )] ( 1a ) and [(η 6 -1,3,5-Me 3 C 6 H 3 )RuCl 2 (Ph 2 AsCH CH 2 )] ( 4a ) undergo KOBu t -promoted intramolecular hydroalkylation in boiling acetonitrile to produce tethered arsinopropylarene−ruthenium(II) complexes 1c and 4c, respectively. The complexes have been characterized by 1 H and 13 C{ 1 H} NMR spectroscopy, elemental analyses, cyclic voltammetry, and in several cases by X-ray crystallography.