2016
DOI: 10.1021/jacs.5b12827
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Accessing Pincer Bis(carbene) Ni(IV) Complexes from Ni(II) via Halogen and Halogen Surrogates

Abstract: This communication describes the two-electron oxidation of ((DIPP)CCC)NiX ((DIPP)CCC = bis(diisopropylphenyl-benzimidazol-2-ylidene)phenyl); X = Cl or Br) with halogen and halogen surrogates to form ((DIPP)CCC)NiX3. These complexes represent a rare oxidation state of nickel, as well as an unprecedented reaction pathway to access these species through Br2 and halogen surrogate (benzyltrimethylammonium tribromide). The Ni(IV) complexes have been characterized by a suite of spectroscopic techniques and can readil… Show more

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Cited by 82 publications
(52 citation statements)
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“…[10][11][12][13][14][15][16][17][18][19][20] By comparison, stoichiometric and catalytic Ni-mediated C-heteroatom bond formation reactions have been developed mostly in the past two decades. [21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36] In the past several years we have employed tetradentate pyridinophane ligands to stabilize uncommon organometallic Pd III/IV and Ni III/IV complexes, [37][38][39][40][41][42][43][44] which can undergo C-C and C-heteroatom bond formation reactions. In addition, we have recently reported the use of the ligand 1,4,7-trimethyl-1,4,7triazacyclonane (Me 3 tacn) to stabilize high-valent Ni III/IV complexes that undergo C-C and C-heteroatom bond formation reactions.…”
Section: Introductionmentioning
confidence: 99%
“…[10][11][12][13][14][15][16][17][18][19][20] By comparison, stoichiometric and catalytic Ni-mediated C-heteroatom bond formation reactions have been developed mostly in the past two decades. [21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36] In the past several years we have employed tetradentate pyridinophane ligands to stabilize uncommon organometallic Pd III/IV and Ni III/IV complexes, [37][38][39][40][41][42][43][44] which can undergo C-C and C-heteroatom bond formation reactions. In addition, we have recently reported the use of the ligand 1,4,7-trimethyl-1,4,7triazacyclonane (Me 3 tacn) to stabilize high-valent Ni III/IV complexes that undergo C-C and C-heteroatom bond formation reactions.…”
Section: Introductionmentioning
confidence: 99%
“…This implies the reversibility of the reaction of 6!7 and similar reactivity was observed for Fouts Ni IV tris(halido) complex. [16] Notably,v an Koten [13a, 17] and others [18] have studied the oxidative additions of halogen molecules to [NCN]-type pincer complexes [Pt II X(NCN)] (X = halide). It was found that for X = Cl or Br,the resulting Pt IV species is stable enough and no reverse reactions back to Pt II precursors were observed.…”
Section: Communicationsmentioning
confidence: 99%
“…Heating the solution of 7 in CDCl 3 at 50 °C for 12 h gave 6 as the major decomposed product in a yield of about 25 % (Supporting Information, Figure S5). This implies the reversibility of the reaction of 6 → 7 and similar reactivity was observed for Fout's Ni IV tris(halido) complex . Notably, van Koten and others have studied the oxidative additions of halogen molecules to [NCN]‐type pincer complexes [Pt II X(NCN)] (X=halide).…”
Section: Figurementioning
confidence: 99%