Tridentate amidophosphine derivatives of the nickel triad: synthesis, characterization, and reactivity of nickel(II), palladium(II), and platinum(II) amide complexes

Fryzuk, Michael D.; MacNeil, Patricia A.; Rettig, Steven J.; Secco, A. S.; Trotter, James

doi:10.1021/om00067a006

Cited by 88 publications

(65 citation statements)

References 0 publications

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“…There appears to be an interaction between the lone pair of electrons and the Ni metal center. The Ni--N bond length of 1.932 (3)A, is consistent with the Ni--N bond length of 1.924 (2)A, found in [NiCIN(SiMe2CH2PPh2)2], (II) (Fryzuk, MacNeil, Rettig, Secco & Trotter, 1982). This interaction is not observed in the complexes , and trans- (Penney, VanderLende, Boncella & Abboud, 1995), where the Ni--N bond lengths are 1.974 (3) and 1.978 (6)A,, respectively._This lengthening of the Ni--N bond by at least 0.04 A is due to the delocalization of the lone pair onto the carbonyl group in compounds (III) and (IV).…”

Section: Pme3 /H (I)supporting

confidence: 86%

trans-[Ni(Me3Ph)(NHPh)(PMe3)2], a Monomeric NiII–Amide Complex

VanderLende¹,

Boncella²,

Abboud³

1995

Acta Crystallogr C

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Section: Pme3 /H (I)supporting

confidence: 86%

trans-[Ni(Me3Ph)(NHPh)(PMe3)2], a Monomeric NiII–Amide Complex

VanderLende¹,

Boncella²,

Abboud³

1995

Acta Crystallogr C

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“…The acetate ligand in 6 is coordinated in an h 1 fashion, a common coordination mode for mononuclear Ni II acetate complexes. [32] The Ni-O distance is slightly shorter in 6 (1.890(3) ) than in 7 (1.946 (2) 2.1703(6) ), [21] [{N(o-C 6 H 4 PPh 2 ) 2 }NiCl] (11, 2.1636(11) ), [25] and [{2,6-bis({dimethylamino}methyl)phenyl}NiCl] (12, 2.2388 (5) ).…”

Section: Structure Of Complexesmentioning

confidence: 99%

“…Our exploration of this ligand in coordination chemistry and catalysis is inspired by previous work on pincer ligands. [21][22][23] We notice particularly the broad applications of pincer phosphine ligands (B and C) in late-transition-metal-mediated small-molecule activation and homogeneous catalysis. [22][23][24][25][26] Pincer amine ligands are less exploited for similar applications.…”

Section: Introductionmentioning

confidence: 99%

Nickel Complexes of a Pincer Amidobis(amine) Ligand: Synthesis, Structure, and Activity in Stoichiometric and Catalytic CC Bond‐Forming Reactions of Alkyl Halides

Vechorkin¹,

Csók²,

Scopelliti³

et al. 2009

Chemistry A European J

109

107

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The synthesis, properties, and reactivity of nickel(II) complexes of a newly developed pincer amidobis(amine) ligand ((Me)NN(2)) are described. Neutral or cationic complexes [((Me)NN(2))NiX] (X = OTf (6), OC(O)CH(3) (7), CH(3)CN (8), OMe (9)) were prepared by salt metathesis or chloride abstraction from the previously reported [((Me)NN(2))NiCl] (1). The Lewis acidity of the {((Me)NN(2))Ni} fragment was measured by the (1)H NMR chemical shift of the coordinated CH(3)CN molecule in 8. Electrochemical measurements on 1 and 8 indicate that the electron-donating properties of NN(2) are similar to those of the analogous amidobis(phosphine) (pnp) ligands. The solid-state structures of 6-8 were determined and compared to those of 1 and [((Me)NN(2))NiEt] (3). In all complexes, the (Me)NN(2) ligand coordinates to the Ni(II) ion in a mer fashion, and the square-planar coordination sphere of the metal is completed by an additional donor. The coordination chemistry of (Me)NN(2) thus resembles that of other three-dentate pincer ligands, for example, pnp and arylbis(amine) (ncn). Reactions of 2 with alkyl monohalides, dichlorides, and trichlorides were investigated. Selective C-C bond formation was observed in many cases. Based on these reactions, efficient Kumada-Corriu-Tamao coupling of unactivated alkyl halides and alkyl Grignard reagents with 1 as the precatalyst was developed. Good yields were obtained for the coupling of primary and secondary iodides and bromides. Double C-C coupling of CH(2)Cl(2) with alkyl Grignard reagents by 1 was also realized. The scope and limitations of these transformations were studied. Evidence was found for a radical pathway in Ni-catalyzed C-C cross-coupling reactions, which involves Ni(II) alkyl intermediates.

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“…1 The first members of this class, namely [N(SiMe 2 CH 2 PR 2 ) 2 ], were described by Fryzuk in 1982 [15][16][17], while the related [N(CH 2 CH 2 PR 2 ) 2 ] ligand was reported in 2006 [18,19]. An important development with respect to [PNP] ligands was the incorporation of ortho-arylene linkers between the ligating atoms, as illustrated in Fig.…”

Section: [J 2 -{[Mepnp Ph ]H}gabr 2 ][Gabrmentioning

confidence: 99%