Solvolysis kinetics of pentaammine(trifluoromethanesulfonato-O) complexes of cobalt(III), rhodium(III), and iridium(III)

Lawrance, Geoffrey A.

doi:10.1021/ic00197a017

Cited by 7 publications

(2 citation statements)

References 4 publications

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“…As they combine a large volume (V̄ = 80.4 and 120 cm 3 mol -1 ) with a relatively low σ-donor strength, their metal salts will be essentially dissociated in solution. Amines readily replace anions such as CF 3 SO 3 - . However, nucleophilicity and volume cannot fully explain the higher reaction rates observed with anions RSO 3 - in comparison to other weakly coordinating anions.…”

Section: Resultsmentioning

confidence: 95%

Developing Transition-Metal Catalysts for the Intramolecular Hydroamination of Alkynes

et al. 1999

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Group 7-12 transition-metal complexes serve as effective catalysts for the regioselective intramolecular hydroamination of aminoalkynes having the general formula RCtC(CH 2 ) n -NH 2 (n ) 3, R ) H, Ph; n ) 4, R ) H) and of 2-(phenylethynyl)aniline. Primary products are pyrrolidines and piperidines bearing an R-alkylidene functionality and 2-phenylindole, respectively. Isomerization yields the corresponding pyrrolines and 1,2-dehydropiperidines. The catalytic properties of the transition-metal complexes depend on the appropriate choice of ligand, solvent, temperature, and counteranion. Principles for identifying the most active transition-metal catalysts for the hydroamination of alkynes and for optimizing the reaction conditions are developed. The X-ray crystal structure of one catalyst, [PdCl(triphos)](CF 3 -SO 3 ), has been determined.

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Section: Resultsmentioning

confidence: 95%

Developing Transition-Metal Catalysts for the Intramolecular Hydroamination of Alkynes

et al. 1999

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“…Rate constants for solvolysis of M(NH3)5(0S02CF3)2+ (M = Co, Rh, Ir) in a range of polar and potentially coordinating solvents have been determined. 206 For all solvents studied with each metal (Table VI) a rate ratio for Co:Rh:Ir of approximately 90:40:1 is preserved, with the progressively slower rate constant from cobalt to iridium arising in the activation entropy term for all solvents except water, suggesting a mechanistic uniqueness for this solvent probably tied to its unique hydrogen-bonding capacity. While the relationships between rate constant and solvent properties have been probed,206 it is the demonstrated ability of alcohols, sulfoxides, amides, nitriles, phosphate esters, and amines to replace CF3S03~readily under mild conditions that is of importance from a synthetic viewpoint.…”

Section: Kinetics Of Substitution Of Coordinated Rso3-mentioning

confidence: 93%