Hemilability of P(X)N-type ligands (X = O, N-H): rollover cyclometalation and benzene C-H activation from (P(X)N)PtMe2 complexes

The thermolyses of ((tBu)P(O)N)PtMe2 (, (tBu)P(O)N = (di-tert-butylphosphinito)pyridine) and ((tBu)P(N-H)N)PtMe2 (, (tBu)P(N-H)N = (di-tert-butylphosphino)-2-aminopyridine) in benzene-d6 were investigated. With ((tBu)P(O)N)PtMe2, the product of a rollover cyclometalation of the pyridyl ring was obse...

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Published in:Dalton transactions : an international journal of inorganic chemistry 2014-08, Vol.43 (31), p.12018-12025
Main Authors: Scheuermann, Margaret L, Grice, Kyle A, Ruppel, Matthew J, Roselló-Merino, Marta, Kaminsky, Werner, Goldberg, Karen I
Format: Article
Language:English
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Summary:The thermolyses of ((tBu)P(O)N)PtMe2 (, (tBu)P(O)N = (di-tert-butylphosphinito)pyridine) and ((tBu)P(N-H)N)PtMe2 (, (tBu)P(N-H)N = (di-tert-butylphosphino)-2-aminopyridine) in benzene-d6 were investigated. With ((tBu)P(O)N)PtMe2, the product of a rollover cyclometalation of the pyridyl ring was observed in 80% yield along with formation of CH4. In contrast, thermolysis of ((tBu)P(N-H)N)PtMe2 resulted in competing rollover cyclometalation and intermolecular benzene C-H activation with production of a mixture of CH4 and CH3D.
ISSN:1477-9234
DOI:10.1039/c4dt01143k