The synthesis and structure of lithium derivatives of the sterically encumbered β-diketiminate ligand [{(2,6-Pri2H3C6)N(CH3)C}2CH]–, and a modified synthesis of the aminoimine precursor

Stender, Matthias; Wright, Robert J.; Eichler, Barrett E.; Prust, Jörg; Olmstead, Marilyn M.; Roesky, Herbert W.; Power, Philip P.

doi:10.1039/b103149j

Cited by 170 publications

(218 citation statements)

References 28 publications

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“…A review of the recent literature revealed a widespread use of chelating, anionic ligands derived by deprotonation of bulky aryl-substituted b-aminoimines such as I and related ligands bearing other flanking Nsubstituents, which have the potential for precise steric and electronic ÔtuningÕ of a reactive metal site. Ligands of this type have been used to support a variety of lowcoordinate transition metal [3][4][5][6][7][8][9][10][11][12][13], main group element [14][15][16][17][18][19][20] and f-element complexes [21,22]. Furthermore, many of these systems have shown great utility in, for example, ring opening polymerisation catalysis [23][24][25][26] or as synthetic mimics for low-coordinate metal environments encountered in biological systems [27][28][29][30].…”

Section: Introductionmentioning

confidence: 99%

Group 1 and 13 complexes of aryl-substituted bis(phosphinimino)methyls

Hill

Hitchcock

Karagouni

2004

Journal of Organometallic Chemistry

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Section: Introductionmentioning

confidence: 99%

Group 1 and 13 complexes of aryl-substituted bis(phosphinimino)methyls

Hill

Hitchcock

Karagouni

2004

Journal of Organometallic Chemistry

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“…complex generated in a non-coordinating solvent (hexane), in which the lithium centers were stabilized by the ligand and its aromatic rings. [36] In sharp contrast to this know example, the lithium centers of complex 4 are stabilized by the β-diketiminate ligand and the fluorine substituents. The tetrahedral coordination geometry of the metal is distorted due to the strain imposed by the six-membered ring of the chelate, and the four-membered ring of the bridging halides.…”

Section: Resultsmentioning

confidence: 93%

Synthesis and structural characterization of LiI, ZnII, CdII, and HgII complexes containing a fluorinated β-diketiminate ligand

Liu¹,

Vieille‐Petit²,

Linden³

et al. 2012

Journal of Organometallic Chemistry

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The reaction of a fluorinated -aminoimine compound ArN]C(Me)CH]C(Me)NHAr (1) (Ar = 2,6-F2C6H3) with n-BuLi in coordinating solvents (Et2O and THF) leads to the solvated complexes [HC(CMeNAr)2]Li(Et2O) (2) and [HC(CMeNAr)2]Li(THF) (3), respectively. They exist as momonuclear complexes featuring lithium atoms in a distorted trigonal planar environment. The same reaction, which was then carried out in a non-coordinated solvent (pentane), provided complex [HC(CMeNAr)2]2Li2 (4). It crystallized as a dinuclear complex in the solid state, featuring lithium atoms in a pseudo-tetrahedral coordination environment. Notably, one fluorine atom of each ligand was involved to stabilize the lithium center. Taking complex 2 as the precursor, a series of group 12 metal complexes were prepared via the reaction with MX2 (M = Zn, Cd, Hg; X = Br, I). The diketiminate zinc complexes [HC(CMeNAr)2]Zn(-I)2Li(Et2O)2 (5) and [HC(CMeNAr)2]Zn(-Br)2Li(Et2O)2 (6) were successfully synthesized and characterized by single crystal X-ray diffraction analysis. When 2 reacted with CdI2, the expected double iodide bridging product [HC(CMeNAr)2]Cd(-I)2Li(Et2O)2 (7a) was only generated in a small amount, with the single iodide bridging complex HC(CMeNAr)2Cd(I)(-I)Li(Et2O)3 (7b) as the major product. These results were unambiguously confirmed by NMR spectroscopy and X-ray crystallography. Next, a mercury complex [HC(CMeNAr)2]Hg(-I)2Li(Et2O) (8) was prepared by using HgI2 as the metal source. Additionally, [HC(CMeNAr)2]ZnEt (9) was also obtained by mixing ligand 1 with Et2Zn. E-mail address: jj.liu209@gmail.com (JL) and xluan@nwu.edu.cn (XL) ABSTRACT

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“…All carbodiimides were purchased from Sigma-Aldrich and used without further purification. The β-diketiminate ligand precursor, ArNHC(Me)CHC(Me)NAr (Ar = 2,6-diisopropylphenyl), [18] heavier alkaline earth amides [M{N(SiMe 3 ) 2 } 2 -(THF) 2 ] (M = Ca, Sr and Ba), [19] and the heteroleptic calcium amide 1 [6a] were prepared by literature procedures.…”

Section: Methodsmentioning

confidence: 99%

Heavier Group‐2‐Element Catalyzed Hydroamination of Carbodiimides

et al. 2008

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The heteroleptic calcium amide [{ArNC(Me)CHC(Me)NAr}Ca{N(SiMe3)2}(THF)] (Ar = 2,6‐diisopropylphenyl) and the homoleptic heavier alkaline earth amides, [M{N(SiMe3)2}2(THF)2] (M = Ca, Sr and Ba) are reported as competent pre‐catalysts for the hydroamination of 1,3‐carbodiimides. Whilst the reaction scope is currently limited to reactions of aromatic amines with 1,3‐dialkylcarbodiimides, in most cases preparations in hydrocarbon solvents proceed rapidly at room temperature with catalyst loadings as low as 0.2 mol‐% and the guanidine reaction products crystallize directly from the reaction mixture. Initial studies are consistent with the intermediacy of heavier group‐2 guanidinate complexes.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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The synthesis and structure of lithium derivatives of the sterically encumbered β-diketiminate ligand [{(2,6-Pri2H3C6)N(CH3)C}2CH]–, and a modified synthesis of the aminoimine precursor

Cited by 170 publications

References 28 publications

Group 1 and 13 complexes of aryl-substituted bis(phosphinimino)methyls

Group 1 and 13 complexes of aryl-substituted bis(phosphinimino)methyls

Synthesis and structural characterization of LiI, ZnII, CdII, and HgII complexes containing a fluorinated β-diketiminate ligand

Heavier Group‐2‐Element Catalyzed Hydroamination of Carbodiimides

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