Synthesis and characterisation of aluminium and magnesium complexes supported by pendant oxalic amidinate ligands

Chen, Chi‐Tien; Huang, C.L.; Tzeng, Yi-Ren; Huang, Bor-Hunn

doi:10.1039/b301744c

Cited by 36 publications

(21 citation statements)

References 44 publications

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“…Type A (Chart 1) has the linkage located on the carbon atoms and could be reached through three ways: (1) by reactions of LiN(SiMe 3 ) 2 and di-or tri-cyanobenzene; 4-6 (2) by combination of dilithio aromatic compounds with the corresponding carbodiimides; 7-10 (3) by condensation of bis(imidoyl) chloride with amines to give the direct connection. 11, 12 Type B, with bridged nitrogen atoms, is derived from the chiral 1,2-diaminocyclohexane and consists of two kinds of derivatives: (1) the traditional silylated benzamidinates and (2) robust nonsilylated amidinates. [13][14][15][16][17] Type C could be obtained by addition reactions of biscarbodiimides with nucleophiles or the silylated diamides with nitriles.…”

Section: Introductionmentioning

confidence: 99%

A convenient route to silyl linked bis(amidinate) ligands and synthesis of group(i) metal derivatives

2006

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A novel type of linked bis(amidinate) ligands (D) were developed successfully. Their lithium derivatives 1-4 were synthesized by treating the silyl-bridged diamines I-IV with two equivalents of LiBu(n) and PhCN in sequence, which underwent a silyl-bridge migration process. In addition, the linked bis(amidinate) configuration proved to be the thermodynamically stable form rather than the mono(amidinate) type by contrasting reaction of I with one equivalent of LiBu(n) and PhCN in sequence.

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Section: Introductionmentioning

confidence: 99%

A convenient route to silyl linked bis(amidinate) ligands and synthesis of group(i) metal derivatives

2006

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“…Since, interest in amidinate supported alkylaluminium species has understandably flourished. 2,[7][8][9][10][11][12][13][14] Despite the implications of this landmark discovery, attempts to soundly identify the catalytic species have not been conclusive. 2,15 However, dinuclear trisalkyl species have been put forward as candidates.…”

Section: Introductionmentioning

confidence: 99%

The syntheses and structures of some main group complexes of the sterically hindered N,N′-bis(2,6-diisopropylphenyl)-4-toluamidinate ligand

2005

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“…Several amidi nate ligands containing electron donating groups in the side chain are documented. [25][26][27][28] The aims of the present study were to design a new non symmetrical amidinate ligand {o MeOC 6 H 4 NC(Ph)N(SiMe 3 )}, in which one of the N atoms contains the ether group capable of coordi nating to the metal atom, as well as to synthesize lithium and yttrium complexes based on this ligand.…”

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New potentially tridentate amidinate ligand {o-MeOC6H4NC(Ph)N(SiMe3)}−. Synthesis and molecular structures of amidinate complexes of lithium [{o-MeOC6H4NC(Ph)N(SiMe3)}Li]2 and yttrium [{o-MeOC6H4NC(Ph)N(SiMe3)}YCl2(THF)2]2

et al. 2011

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The reaction of lithium silylamide [{o MeOC 6 H 4 N(SiMe 3 )}Li(OEt 2 )] 2 with 2 equiv. of benzonitrile in THF at ~20 °C affords the lithium derivative of the new tridentate amidinate ligand [{o MeOC 6 H 4 NC(Ph)N(SiMe 3 )}Li] 2 . The X ray diffraction study showed that this complex has a dimeric structure due to the coordination of the N atoms and the ether group of one amid inate ligand to different Li atoms. The reaction of anhydrous YCl 3 with the resulting complex in THF gives the monoamidinate complex [{o MeOC 6 H 4 NC(Ph)N(SiMe 3 )}YCl 2 (THF) 2 ] 2 re gardless of the reagent ratio. The latter has a dimeric structure in the crystalline state as a result of the presence of two μ 2 bridging Cl atoms that link Y atoms. The ether groups of the amid inate ligands are not involved in the metal-ligand interaction.The amidinate ligands [RC(NR´) 2 ] -belonging to monoanionic four electron ligands, in which the negative charge in delocalized over the NCN group, have attracted researchers' attention in the last three decades due to di verse coordination properties. In addition, the obvious ad vantages of amidinate ligands are that their electronic and steric properties can be easily modified by varying the sub stituents both at the N atoms and the central C atom, as well as that the starting reagents for their preparation are available and relatively cheap. Recent studies have shown the great synthetic potential of amidinate ligands in coor dination chemistry of a large number of elements. 1-6 Data on amidinate ligands in organolanthanide chemistry pub lished in the works of Edelmann 7-11 and Teuben 12-17 have greatly stimulated the development of this field and made it possible to synthesize and characterize various classes of their derivatives. Highly reactive alkyl, cationic alkyl, and hydride complexes of rare earth metals show the ability to catalyze a series of transformations of unsaturat ed substrates, such as polymerization of olefins 15,16 and dienes, 18 selective dimerization of monosubstituted acetyl enes, 19 hydroboration, 20 hydrosilylation, 21 and hydro amination 22 of olefins.It is known that the stability and reactivity of organic derivatives of rare earth metals are determined to a large extent by the coordinative and steric saturation of the metal coordination sphere. Therefore, considerable efforts are currently focused on searching for new types of ligand systems, which can stabilize metal complexes and provide additional ways to design the coordination environment of the central metal atom and control the reactivity. 23,24 One of approaches to this problem is based on the intro duction of additional groups, which have Lewis base prop erties and can be coordinated to a metal atom, into the ligand system, resulting in the saturation of the coordina tion sphere and a change in its geometry. Several amidi nate ligands containing electron donating groups in the side chain are documented. 25-28 The aims of the present study were to design a new non symmetrical amidinate ligand {o MeOC 6 H 4 NC(Ph)N(S...

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Synthesis and characterisation of aluminium and magnesium complexes supported by pendant oxalic amidinate ligands

Cited by 36 publications

References 44 publications

A convenient route to silyl linked bis(amidinate) ligands and synthesis of group(i) metal derivatives

A convenient route to silyl linked bis(amidinate) ligands and synthesis of group(i) metal derivatives

The syntheses and structures of some main group complexes of the sterically hindered N,N′-bis(2,6-diisopropylphenyl)-4-toluamidinate ligand

New potentially tridentate amidinate ligand {o-MeOC6H4NC(Ph)N(SiMe3)}−. Synthesis and molecular structures of amidinate complexes of lithium [{o-MeOC6H4NC(Ph)N(SiMe3)}Li]2 and yttrium [{o-MeOC6H4NC(Ph)N(SiMe3)}YCl2(THF)2]2

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