104155-44-4Relevant academic research and scientific papers
Menschutkin type amine alkylations involving ethyl transfer from platinum (II) chelate complexes of o-(diphenylphosphino)thiophenetole
Benefiel, Annamarie,Roundhill, D. Max
, p. 4027 - 4031 (2008/10/08)
The compound o-Ph2PC6H4SEt has been used as a chelate ligand to synthesize the platinum(II) complexes cis-[Pt(o-Ph2PC6H4SEt)2](BF 4)2 and cis-[Pt(o-Ph2PC6H4S)(o-Ph2PC 6H4SEt)]BF4. The complex cis-Pt(o-Ph2PC6H4SEt)22+ reacts with amines to give cis-Pt(o-Ph2PC6H4S)(o-Ph2PC 6H4SEt)+ and then Pt(o-Ph2PC6H4S)2. The rate laws are first order in both platinum complex and amine. In acetonitrile solvent the rate constants and thermodynamic parameters (ΔH? and ΔS?) have been obtained for the first reaction step with dibenzylamine, butylamine, dibutylamine, tributylamine, diethylamine, and triethylamine. In DMF solvent the analogous data have been measured for the second step by using butylamine, dibutylamine, and tributylamine. The ΔH? (13-18 kcal mol-1) and ΔS? (-12 to -31 cal K-1 mol-1) values are in the range expected for a Menschutkin type SN2 alkylation reaction. The reaction rates decrease in the amine sequence primary > secondary > tertiary, but for benzylamines the rate only differs by a factor of 5 from benzylamine to tribenzylamine.
