1073295-97-2Relevant academic research and scientific papers
Oxidative dehydrogenation of tris(o-isopropylphenyl)phosphines by platinum complexes
Baber, Angharad,Fan, Cheng,Norman, David W.,Orpen, A. Guy,Pringle, Paul G.,Wingad, Richard L.
, p. 5906 - 5910 (2008)
The binuclear cyclometalates [Pt2Cl2{2-CMe 2C6H4P(C6H4(2- iPr))2}2] (1a) and [Pt2Cl 2[2-CMe2C6H3(4-OMe)P(C 6H3(2-iPr)(4-OMe))2}2] (1b) react with CHCl2CHCl2 to give the corresponding mononuclear phosphine-alkene chelates [PtCl2 {2-CH 2=CMeC6H4P(C6H4(2- iPr))2}] (2a) and [PtCl2 [2-CH 2=CMeC6H3(4-OMe)P(C6H 3(2-iPr)(4-OMe))2}] (2b). The product 2a can also be formed directly from [PtCl2(NCtBu)2] and La in CHCl2CHCl2 or by addition of SO 2Cl2 to 1a. Addition of an excess of SO2Cl 2 to 1b gave [PtCl2 {2-CH2=CMeC 6H3(4-OMe)P(C6H2(2- iPr)(4-OMe)(5-Cl))2}] (3b), a derivative of 2b featuring metachlorine substituents on the terminal P groups as a result of electrophilic aromatic substitution. A mechanism for the conversion of 1a,b to 2a,b is proposed involving an electrophilic alkyl C-H activation by a coordinatively unsaturated platinum(IV) species. The mechanism is supported by the isolation of the diplatinum(IV) cyclometalate [Pt2Cl2 {2-CH 2C6H3(4-OMe)P(C6H 3(2-Me)(4-OMe))2}] as a mixture of syn and anti isomers 5b and 5b′. The crystal structures of 2a and 3b have been determined.
