(Alkyliminomethyl)phenylamido and related complexes of zirconium and titanium

Porter, Robin M.; Winston, Scott; Danopoulos, Andreas A.; Hursthouse, Michael B.

doi:10.1039/b202471c

Cited by 16 publications

(13 citation statements)

References 29 publications

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“…β‐Diketiminato Li complexes are often used as ligand transfer reagents in the preparation of transition‐metal coordination complexes because of their high yield lithiation and transmetalation activities , . For example, metal β‐diketiminate complexes with rare‐earth or d‐block transition metals can be synthesized by the reaction of β‐diketiminato Li complexes with their corresponding metal halides , , . Indeed, there are few studies describing the preparation of Li complexes bearing unsymmetrical N ‐aryl‐ N′ ‐alkyl β‐diketimines (UNAAD) , .…”

Section: Introductionmentioning

confidence: 99%

Improved Synthesis of Unsymmetrical N‐Aryl‐N′‐alkylpyridyl ß‐Diketimines Using Molecular Sieves and their Lithium Complexes

et al. 2018

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The synthesis of unsymmetrical β‐diketimines with N‐aryl‐N′‐alkyl substitution require at least two condensation steps and tedious purification procedures. An improvement in the preparation of four unsymmetrical N‐aryl‐N′‐alkylpyridyl β‐diketimine ligands (HL1–HL4) using 5‐Å molecular sieves is reported. The synthesis of four Li complexes (LiL1, LiL2, LiL3, and LiL4) containing N‐aryl‐N′‐alkylpyridyl β‐diketimines ligands is also presented. All four Li complexes were fully characterized by 1H NMR spectroscopic, 13C NMR spectroscopic, and elemental analyses. X‐ray structure analysis and spectroscopic results indicate that the Li β‐diketimine structures and ligand binding modes are governed by the bulkiness of the N‐aryl substituent and the length of the pyridyl arm of the N‐aryl‐N′‐alkyl β‐diketiminate ligand.

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Section: Introductionmentioning

confidence: 99%

Improved Synthesis of Unsymmetrical N‐Aryl‐N′‐alkylpyridyl ß‐Diketimines Using Molecular Sieves and their Lithium Complexes

et al. 2018

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“…The N1, N2, C1, C2 fragment remains essentially planar with twist angles below 10°. The latter group (3,4,(9)(10)(11)(12) shows a distorted ligand mean plane with twist angles above 15°, significant differences in Zr-C2/4 distances (>0.2 Å), in Zr-C2/4-C1/5 angles (>25°) and increased C-N-C2/ 4-C1/5 torsion angles (>15°).…”

Section: Zr -C3 [å] Bending Out Of the Mean Ligand Planementioning

confidence: 96%

“…In mono-[2-9] and bis(diketiminate) complexes of zirconium [4,6,7,10], as well as in complexes with the related iminomethylaniline [11,12] or azaallylpyridine ligands [13,14], the ligand is bound via the two nitrogen lone pairs with the metal found in the ligand mean plane (Scheme 1, A). Steric crowding around the metal center, in particular with sterically demanding substituents on nitrogen, results in a displacement of the metal out of the ligand mean plane (Scheme 1, B) [1,3].…”

Section: Introductionmentioning

confidence: 99%

Coordination modes in zirconium β-diketiminate complexes

El-Zoghbi

Verguet

Oguadinma

et al. 2010

Inorganic Chemistry Communications

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“…Similar bond distances have been observed in the structures of the silylamido analogues. 5 The metrical data around the imine carbons indicate a planar geometry with CN double bonds in the normal range [1.269(6)-1.291( 6) Å]. In solution L xyl Li exists as an equilibrium mixture of two species with differing degrees of aggregation (possibly dimeric and trimeric).…”

Section: Introductionmentioning

confidence: 99%

“…This is evidenced by the 1 H, 13 We have recently embarked on an investigation of the isoelectronic amido analogues of the salicylaldiminato, (R 2 = H), and salicylketiminato, (R 2 = Me), ligands (II in Scheme 1, R 1 = SiMe 3 ). 5 These are related to the versatile -diketiminato (nacnac) ligands…”

Section: Introductionmentioning

confidence: 99%

o-(Cyclohexyliminoethyl)(arylamido)benzene and related complexes of zirconium and titanium. The non-innocence of the ketimino functionality

Porter

Danopoulos

2004

Dalton Trans.

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N-Arylamido complexes of zirconium in which the amido functional group is attached to an o-(alkyliminoethyl) substituted aromatic ring, have been synthesised by salt elimination reactions and characterised by spectroscopic and diffraction methods; they are analogous to the N-silylamido species recently reported (Dalton Trans., 2002, 3290-3299). The ligands 2-[CyN=C(CH(3))]C(6)H(4)N(H)(xyl), L(xyl)H, and 2-[CyN=C(CH(3))]C(6)H(4)N(H)(mes) L(mes)H, Cy = C(6)H(11), xyl = 3,5-Me(2)C(6)H(3) mes = 2,4,6-Me(3)C(6)H(2), were prepared in good yields by Buchwald-Hartwig amination of the arylbromides with 2-[CyN=C(CH(3))]C(6)H(4)NH(2). Reaction of L(mes)Li with Zr(NEt(2))(2)Cl(2)(thf)(2) gave after chloride substitution the arylamido ketimino complex L(mes)Zr(NEt(2))(2)Cl 1; variable amounts of the arylamido vinylamido complex 2 were also obtained. Interaction of L(mes)Li or L(xyl)Li with Ti(NMe(2))(2)Cl(2) gave rise to the tripodal bis-amido amino complexes 5 and 6 possibly formed by ligand rearrangement involving migration of the dimethylamido group to the ketimino carbon.

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(Alkyliminomethyl)phenylamido and related complexes of zirconium and titanium

Cited by 16 publications

References 29 publications

Improved Synthesis of Unsymmetrical N‐Aryl‐N′‐alkylpyridyl ß‐Diketimines Using Molecular Sieves and their Lithium Complexes

Improved Synthesis of Unsymmetrical N‐Aryl‐N′‐alkylpyridyl ß‐Diketimines Using Molecular Sieves and their Lithium Complexes

Coordination modes in zirconium β-diketiminate complexes

o-(Cyclohexyliminoethyl)(arylamido)benzene and related complexes of zirconium and titanium. The non-innocence of the ketimino functionality

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