Synthesis, characterization and ethylene reactivity of 2-diphenylphosphanylbenzamido nickel complexes

Dalton Transactions : an International Journal of Inorganic Chemistry
Heon Yong KwonYoung Keun Chung

Abstract

Addition of primary amines to N-[2-(diphenylphosphanyl)benzoyloxy]succinimide affords 2-diphenylphosphanylbenzamides, Ph2PC6H4C(O)NHR (R = C(CH3)3, 3; R = H, 4; R = CH2CH2CH3, 5; R = CH(CH3)2, 6). Addition of NiCl(eta3-CH2C6H5)(PMe3) to the deprotonated potassium salts of the amides and subsequent treatment of two equivalents of B(C6F5)3 to the resulting products furnishes eta3-benzyl zwitterionic nickel(II) complexes, [Ph2PC6H4C(O)NR-kappa2N,P]Ni(eta3-CH2C6H5) (R = C6H5, 9; R = C(CH3)3, 10; R = H, 11; R = CH2CH2CH3, 12; R = CH(CH3)2, 13). Solid structures of 9, 11, 13 and the intermediate eta1-benzyl nickel(II) complexes, [Ph2PC6H4C(O)NR-kappa2N,P]Ni(eta1-CH2C6H5)(PMe3) (R = C6H5, 7; R = C(CH3)3, 8) were determined by X-ray crystallography. When ethylene is added to the eta3-benzyl zwitterionic nickel(II) complexes, butene is obtained by the complexes 9-12 but complex 13 provides very high molecular-weight branched polyethylene (Mw, approximately 1300000) with excellent activity (up to 5200 kg mol-1 h-1 at 100 psi gauge).

Citations

Jun 4, 2011·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Jennifer K AngelosanteChristopher J A Daley
Mar 30, 2012·Chemical Society Reviews·Petr Stěpnička
Jun 15, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Junye LiHongjian Sun
Dec 22, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Daisuke Takeuchi
Sep 1, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Laura Ortiz de la TablaJuan Cámpora
Aug 8, 2009·Accounts of Chemical Research·Brycelyn M Boardman, Guillermo C Bazan

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