53753-58-5Relevant articles and documents
Study of the Reactivity of the [(PE1CE2P)Ni(II)] (E1, E2 = O, S) Pincer System with Acetonitrile and Base: Formation of Cyanomethyl and Amidocrotononitrile Complexes versus Ligand Decomposition by P-S Bond Activation
Hasche, Patrick,Spannenberg, Anke,Beweries, Torsten
, p. 4508 - 4515 (2019/11/14)
Nickel(II) chloride complexes with PE1CE2P (E = O, S) pincer ligands were used as precursors for the generation of cyanomethyl complexes in order to investigate the influence of variations (O vs S) in the side arms of the ligands on reactivity and stability of such compounds. In this regard, five hitherto unknown Ni(II) compounds were synthesized and fully characterized. Reaction of the Ni(II) chloride complex [(iPrPOCSPiPr)NiCl] (2-Cl) with 1 equiv of base and nitrile furnishes the cyanomethyl complex [(iPrPOCSPiPr)NiCH2CN] (2-CM). Increase of the amount of base and nitrile results in the formation of 3-amidocrotononitrile complexes [(iPrPOCOPiPr)NiNHC(CH3)CHCN] (1-ACN) and [(iPrPOCSPiPr)NiNHC(CH3)CHCN] (2-ACN). In contrast, similar reactions of the bis(thiophosphinite) complex 3-Cl resulted in formation of a tetranuclear Ni cluster (4) or a dinuclear 1,3-dithiolate-bridged PSCSP complex 5 by unexpected cleavage of P-S bonds of the pincer ligand.