Synthesis of ruthenium phenylindenylidene, carbyne, allenylidene and vinylmethylidene complexes from (PPh3)3−4RuCl2: A mechanistic and structural investigation

Alicia Beatty; Erika A. Shaffer; Edward J. Valente; Hans-Jorg Schanz

doi:10.1016/j.jorganchem.2007.08.005

Synthesis of ruthenium phenylindenylidene, carbyne, allenylidene and vinylmethylidene complexes from (PPh3)3−4RuCl2: A mechanistic and structural investigation

Alicia Beatty, Erika A. Shaffer, Edward J. Valente, Hans-Jorg Schanz

University of Missouri-St. Louis

Research output: Contribution to journal › Article › peer-review

Abstract

<div class="line" id="line-9"> <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> The reaction of (Ph <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 3 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> P) <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 3 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> RuCl <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 2 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'>  with 1,1-diphenyl-2-propyn-1-ol was investigated in various solvents. The reaction in thf under reflux is reported to produce the (PPh <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 3 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> ) <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 2 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> Cl <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 2 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> Ru(3-phenylindenylidene) complex (3) which has undergone rearrangement of the allenylidene C <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 3 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> -spine. We have improved the reliability of the reported synthesis by adding acetyl chloride which converts the formed water of the reaction and thus increases the acidity of the reaction solution. Without the additive, we observed the exclusive formation of an intermediate of the transformation and identified it as dinuclear (PPh <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 3 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> ) <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 2 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> ClRu(μ-Cl) <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 3 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> (PPh <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 3 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> ) <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 2 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> Ru <img src="https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/16/entities/dbnd"/> <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> C <img src="https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/16/entities/dbnd"/> <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> C <img src="https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/16/entities/dbnd"/> <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> CPh <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 2 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'>  complex (5). The reaction of (Ph <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 3 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> P) <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 3−4 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> RuCl <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 2 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'>  with 1,1-diphenyl-2-propyn-1-ol in CH <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 2 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> Cl <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 2 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'>  or C <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 2 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> H <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 4 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> Cl <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 2 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'>  under reflux in the presence of excess conc. aqueous HCl afforded the new, neutral (PPh <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 3 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> ) <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 2 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> Cl <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 3 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> Ru <img src="https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/16/entities/tbnd"/> <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> C–CH <img src="https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/16/entities/dbnd"/> <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> CPh <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 2 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'>  carbyne complex (7), an HCl adduct of previously elusive (PPh <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 3 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> ) <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 2 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> Cl <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 2 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> Ru <img src="https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/16/entities/dbnd"/> <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> C <img src="https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/16/entities/dbnd"/> <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> C <img src="https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/16/entities/dbnd"/> <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> CPh <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 2 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'>  complex 6 in high yields. In contrast to the formation of complex 3, the reaction in a non-coordinating solvent did not afford the rearrangement of the allenylidene C <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 3 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> -spine. Complex 7 was converted into complex 3 in thf under reflux under loss of a molecule HCl. Complex 7 was converted with triethylamine under loss of HCl to complex 6. Pentacoordinate complex 6 was crystallized in the presence of O-donor ligands (EtOH, MeOH and H <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 2 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> O) to give hexacoordinate (PPh <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 3 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> ) <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 2 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> Cl <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 2 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> (ROH)Ru <img src="https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/16/entities/dbnd"/> <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> C <img src="https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/16/entities/dbnd"/> <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> C <img src="https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/16/entities/dbnd"/> <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> CPh <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 2 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'>  (R = H, CH <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 3 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> , C <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 2 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> H <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 5 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> ) complexes (9)–(11) with the O-donor coordinating in  <i style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> trans <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> -position to the allenylidene moiety. The reaction of complex 7 with 2 equiv. of 4-( <i style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> N <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> , <i style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> N <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> -dimethylamino)pyridine (DMAP) gave hexacoordinate (PPh <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 3 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> ) <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 2 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> Cl <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 2 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> (DMAP)Ru <img src="https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/16/entities/dbnd"/> <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> C <img src="https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/16/entities/dbnd"/> <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> C <img src="https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/16/entities/dbnd"/> <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> CPh <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 2 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> complex (12) with one molecule DMAP also coordinating in  <i style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> trans <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> -position to the allenylidene group. Methanol and acetic acid in the absence of strong bases afforded the Fischer-carbene complexes (PPh <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 3 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> ) <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 2 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> Cl <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 2 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> Ru <img src="https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/16/entities/dbnd"/> <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> C(OCH <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 3 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> )–CH <img src="https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/16/entities/dbnd"/> <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> CPh <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 2 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'>  (14) and (PPh <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 3 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> ) <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 2 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> Cl <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 2 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> Ru <img src="https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/16/entities/dbnd"/> <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> C(OAc)–CH <img src="https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/16/entities/dbnd"/> <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'> CPh <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 13.5px;'> 2 <span style='color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px;'>  (15) where the nucleophile added to the α-carbon atom. The structures of complexes 5, 7, 9–11, 14, and 15 were solved via X-ray crystallography. </div>

Original language	American English
Journal	Journal of Organometallic Chemistry
Volume	692
DOIs	https://doi.org/10.1016/j.jorganchem.2007.08.005
State	Published - Nov 1 2007

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Chemistry

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@article{7a6bc22c4d01417a8360263d8f4c27a8,

title = "Synthesis of ruthenium phenylindenylidene, carbyne, allenylidene and vinylmethylidene complexes from (PPh3)3−4RuCl2: A mechanistic and structural investigation",

abstract = " The reaction of (Ph 3 P) 3 RuCl 2  with 1,1-diphenyl-2-propyn-1-ol was investigated in various solvents. The reaction in thf under reflux is reported to produce the (PPh 3 ) 2 Cl 2 Ru(3-phenylindenylidene) complex (3) which has undergone rearrangement of the allenylidene C 3 -spine. We have improved the reliability of the reported synthesis by adding acetyl chloride which converts the formed water of the reaction and thus increases the acidity of the reaction solution. Without the additive, we observed the exclusive formation of an intermediate of the transformation and identified it as dinuclear (PPh 3 ) 2 ClRu(μ-Cl) 3 (PPh 3 ) 2 Ru C C CPh 2  complex (5). The reaction of (Ph 3 P) 3−4 RuCl 2  with 1,1-diphenyl-2-propyn-1-ol in CH 2 Cl 2  or C 2 H 4 Cl 2  under reflux in the presence of excess conc. aqueous HCl afforded the new, neutral (PPh 3 ) 2 Cl 3 Ru C–CH CPh 2  carbyne complex (7), an HCl adduct of previously elusive (PPh 3 ) 2 Cl 2 Ru C C CPh 2  complex 6 in high yields. In contrast to the formation of complex 3, the reaction in a non-coordinating solvent did not afford the rearrangement of the allenylidene C 3 -spine. Complex 7 was converted into complex 3 in thf under reflux under loss of a molecule HCl. Complex 7 was converted with triethylamine under loss of HCl to complex 6. Pentacoordinate complex 6 was crystallized in the presence of O-donor ligands (EtOH, MeOH and H 2 O) to give hexacoordinate (PPh 3 ) 2 Cl 2 (ROH)Ru C C CPh 2  (R = H, CH 3 , C 2 H 5 ) complexes (9)–(11) with the O-donor coordinating in  trans -position to the allenylidene moiety. The reaction of complex 7 with 2 equiv. of 4-( N , N -dimethylamino)pyridine (DMAP) gave hexacoordinate (PPh 3 ) 2 Cl 2 (DMAP)Ru C C CPh 2 complex (12) with one molecule DMAP also coordinating in  trans -position to the allenylidene group. Methanol and acetic acid in the absence of strong bases afforded the Fischer-carbene complexes (PPh 3 ) 2 Cl 2 Ru C(OCH 3 )–CH CPh 2  (14) and (PPh 3 ) 2 Cl 2 Ru C(OAc)–CH CPh 2  (15) where the nucleophile added to the α-carbon atom. The structures of complexes 5, 7, 9–11, 14, and 15 were solved via X-ray crystallography. ",

author = "Alicia Beatty and Shaffer, {Erika A.} and Valente, {Edward J.} and Hans-Jorg Schanz",

note = "The reaction of (Ph 3P) 3RuCl 2 with 1,1-diphenyl-2-propyn-1-ol was investigated in various solvents. The reaction in thf under reflux is reported to produce the (PPh 3) 2Cl 2Ru(3-phenylindenylidene) complex ( 3) which has undergone rearrangement of the allenylidene C 3-spine.",

year = "2007",

month = nov,

day = "1",

doi = "10.1016/j.jorganchem.2007.08.005",

language = "American English",

volume = "692",

journal = "Journal of Organometallic Chemistry",

}

TY - JOUR

T1 - Synthesis of ruthenium phenylindenylidene, carbyne, allenylidene and vinylmethylidene complexes from (PPh3)3−4RuCl2: A mechanistic and structural investigation

AU - Beatty, Alicia

AU - Shaffer, Erika A.

AU - Valente, Edward J.

AU - Schanz, Hans-Jorg

N1 - The reaction of (Ph 3P) 3RuCl 2 with 1,1-diphenyl-2-propyn-1-ol was investigated in various solvents. The reaction in thf under reflux is reported to produce the (PPh 3) 2Cl 2Ru(3-phenylindenylidene) complex ( 3) which has undergone rearrangement of the allenylidene C 3-spine.

PY - 2007/11/1

Y1 - 2007/11/1

N2 - The reaction of (Ph 3 P) 3 RuCl 2  with 1,1-diphenyl-2-propyn-1-ol was investigated in various solvents. The reaction in thf under reflux is reported to produce the (PPh 3 ) 2 Cl 2 Ru(3-phenylindenylidene) complex (3) which has undergone rearrangement of the allenylidene C 3 -spine. We have improved the reliability of the reported synthesis by adding acetyl chloride which converts the formed water of the reaction and thus increases the acidity of the reaction solution. Without the additive, we observed the exclusive formation of an intermediate of the transformation and identified it as dinuclear (PPh 3 ) 2 ClRu(μ-Cl) 3 (PPh 3 ) 2 Ru C C CPh 2  complex (5). The reaction of (Ph 3 P) 3−4 RuCl 2  with 1,1-diphenyl-2-propyn-1-ol in CH 2 Cl 2  or C 2 H 4 Cl 2  under reflux in the presence of excess conc. aqueous HCl afforded the new, neutral (PPh 3 ) 2 Cl 3 Ru C–CH CPh 2  carbyne complex (7), an HCl adduct of previously elusive (PPh 3 ) 2 Cl 2 Ru C C CPh 2  complex 6 in high yields. In contrast to the formation of complex 3, the reaction in a non-coordinating solvent did not afford the rearrangement of the allenylidene C 3 -spine. Complex 7 was converted into complex 3 in thf under reflux under loss of a molecule HCl. Complex 7 was converted with triethylamine under loss of HCl to complex 6. Pentacoordinate complex 6 was crystallized in the presence of O-donor ligands (EtOH, MeOH and H 2 O) to give hexacoordinate (PPh 3 ) 2 Cl 2 (ROH)Ru C C CPh 2  (R = H, CH 3 , C 2 H 5 ) complexes (9)–(11) with the O-donor coordinating in  trans -position to the allenylidene moiety. The reaction of complex 7 with 2 equiv. of 4-( N , N -dimethylamino)pyridine (DMAP) gave hexacoordinate (PPh 3 ) 2 Cl 2 (DMAP)Ru C C CPh 2 complex (12) with one molecule DMAP also coordinating in  trans -position to the allenylidene group. Methanol and acetic acid in the absence of strong bases afforded the Fischer-carbene complexes (PPh 3 ) 2 Cl 2 Ru C(OCH 3 )–CH CPh 2  (14) and (PPh 3 ) 2 Cl 2 Ru C(OAc)–CH CPh 2  (15) where the nucleophile added to the α-carbon atom. The structures of complexes 5, 7, 9–11, 14, and 15 were solved via X-ray crystallography.

AB - The reaction of (Ph 3 P) 3 RuCl 2  with 1,1-diphenyl-2-propyn-1-ol was investigated in various solvents. The reaction in thf under reflux is reported to produce the (PPh 3 ) 2 Cl 2 Ru(3-phenylindenylidene) complex (3) which has undergone rearrangement of the allenylidene C 3 -spine. We have improved the reliability of the reported synthesis by adding acetyl chloride which converts the formed water of the reaction and thus increases the acidity of the reaction solution. Without the additive, we observed the exclusive formation of an intermediate of the transformation and identified it as dinuclear (PPh 3 ) 2 ClRu(μ-Cl) 3 (PPh 3 ) 2 Ru C C CPh 2  complex (5). The reaction of (Ph 3 P) 3−4 RuCl 2  with 1,1-diphenyl-2-propyn-1-ol in CH 2 Cl 2  or C 2 H 4 Cl 2  under reflux in the presence of excess conc. aqueous HCl afforded the new, neutral (PPh 3 ) 2 Cl 3 Ru C–CH CPh 2  carbyne complex (7), an HCl adduct of previously elusive (PPh 3 ) 2 Cl 2 Ru C C CPh 2  complex 6 in high yields. In contrast to the formation of complex 3, the reaction in a non-coordinating solvent did not afford the rearrangement of the allenylidene C 3 -spine. Complex 7 was converted into complex 3 in thf under reflux under loss of a molecule HCl. Complex 7 was converted with triethylamine under loss of HCl to complex 6. Pentacoordinate complex 6 was crystallized in the presence of O-donor ligands (EtOH, MeOH and H 2 O) to give hexacoordinate (PPh 3 ) 2 Cl 2 (ROH)Ru C C CPh 2  (R = H, CH 3 , C 2 H 5 ) complexes (9)–(11) with the O-donor coordinating in  trans -position to the allenylidene moiety. The reaction of complex 7 with 2 equiv. of 4-( N , N -dimethylamino)pyridine (DMAP) gave hexacoordinate (PPh 3 ) 2 Cl 2 (DMAP)Ru C C CPh 2 complex (12) with one molecule DMAP also coordinating in  trans -position to the allenylidene group. Methanol and acetic acid in the absence of strong bases afforded the Fischer-carbene complexes (PPh 3 ) 2 Cl 2 Ru C(OCH 3 )–CH CPh 2  (14) and (PPh 3 ) 2 Cl 2 Ru C(OAc)–CH CPh 2  (15) where the nucleophile added to the α-carbon atom. The structures of complexes 5, 7, 9–11, 14, and 15 were solved via X-ray crystallography.

UR - https://www.sciencedirect.com/science/article/abs/pii/S0022328X07005840

U2 - 10.1016/j.jorganchem.2007.08.005

DO - 10.1016/j.jorganchem.2007.08.005

M3 - Article

VL - 692

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

ER -

Synthesis of ruthenium phenylindenylidene, carbyne, allenylidene and vinylmethylidene complexes from (PPh3)3−4RuCl2: A mechanistic and structural investigation

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