Synthesis and structures of lithium, aluminium, gallium and lanthanide amidinates containing a γ-pendant amine functionality

Doyle, David J.; Gun’ko, Yurii K.; Hitchcock, Peter B.; Läppert, Michael F.

doi:10.1039/b005824f

Cited by 53 publications

(31 citation statements)

References 22 publications

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“…Unexpectually, the reaction afforded 2:1 ratio product [(1R,2R)-(À)-1-[NC(Ph)N(SiMe 3 )]-2-(NHSiMe 3 )-C 6 H 10 ] 2 -ZrCl 2 (3). 3 is an unbridged bis(amidinate) zirconium complex, where the pendant amine groups dissociate and this differs from our prediction and some relevant work, in which a lone pair of electrons of pendant amine groups coordinates to the central metals forming a tridentate coordinated environment [14]. Similarly, when reacted with Ti(OiPr) 2 Cl 2 in THF, Li These molecular structure results arose our interest to develop new coordination model.…”

Section: Resultscontrasting

confidence: 57%

“…of nBuLi in hexane. We anticipated that this dianionic amido-amidinate ligand Li[L 2 ] will produce a new type of tridentate fashion where the amidinate fragment bonded to the central metal with g 3 -p bond, and at the same time the pendant amide group forming a r bond, compared to the lone pair of electrons of pendant amine groups coordinated to the central metals [14]. The reaction of Li 2 [L 2 ] with Ti(OiPr) 2 Cl 2 in hexane yielded a new complex of [9a].…”

Section: Resultsmentioning

confidence: 99%

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Synthesis and structural studies of some titanium and zirconium complexes with chiral bis(amide), amidinate or bis(amidinate) ligands

Huang

Weng

et al. 2006

Journal of Organometallic Chemistry

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Section: Resultscontrasting

confidence: 57%

Section: Resultsmentioning

confidence: 99%

Synthesis and structural studies of some titanium and zirconium complexes with chiral bis(amide), amidinate or bis(amidinate) ligands

Huang

Weng

et al. 2006

Journal of Organometallic Chemistry

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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.…”

mentioning

confidence: 99%

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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“…They can also be incorporated as functionality in polydentate ligand systems. Examples have been reported recently on the synthesis and complexation chemistry of monoanionic tridentate amidinate Lewis base and dianionic tetradentate bis(amidinate) ligands . A more sterically hindered amidinate is required or amidinates that can give additional electronic stabilization to the highly electronically unsaturated central metal atoms are required.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Characterization, and Magnetic Properties of Iron Complexes Bearing Polydentate Nitrogen Ligands

Bai

et al. 2017

Zeitschrift anorg allge chemie

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Four iron complexes {[PhN(CH 2 ) 2 NH(SiMe 3 )] 4 FeLi·Et 2 O (1), [PhN(CH 2 ) 3 NSiMe 3 ] 2 FeLi(Et 2 O) (2), [PhN(CH 2 ) 2 NCH(Ph)NSi-Me 3 ] 2 FeLi(Et 2 O) 2 (3), and [PhN(CH 2 ) 3 NCH(Ph)NSiMe 3 ] 2 FeLi(Et 2 O) 2 (4)} with polydentate nitrogen ligands were synthesized and structurally characterized by X-ray crystallography. The X-ray structures of 737 complexes 1-4 show that they crystallize in three different systems. The magnetic properties of 1-4 were investigated. The magnetization trends of magnetic field intensity show the curves of Type-S, illustrating those complexes 1-4 are superparamagnetic.

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Synthesis and structures of lithium, aluminium, gallium and lanthanide amidinates containing a γ-pendant amine functionality

Cited by 53 publications

References 22 publications

Synthesis and structural studies of some titanium and zirconium complexes with chiral bis(amide), amidinate or bis(amidinate) ligands

Synthesis and structural studies of some titanium and zirconium complexes with chiral bis(amide), amidinate or bis(amidinate) ligands

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

Synthesis, Characterization, and Magnetic Properties of Iron Complexes Bearing Polydentate Nitrogen Ligands

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