β-diiminato titanium complexes with varying fluorine substitution patterns on the N-aryl moiety: probing the effect of ligand substitution on ethylene polymerization

Li, Tingcheng; Wen, Shangsheng; Ai, Haitao; You, Qingliang; Zhang, Aiqing; Xie, Guangyong

doi:10.1007/s10965-014-0631-0

Cited by 16 publications

(7 citation statements)

References 51 publications

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“…The phosphine functionalized β‐diketimine ligand ( 1 ) was obtained by a two‐step synthesis route in a multigram scale (Scheme ). In the first step, a fluorine functionalized NacNac ligand (FNac‐H) was formed by a condensation reaction between acetylacetone and 2‐fluoroaniline in refluxing toluene . Subsequently, FNac‐H was reacted with freshly prepared KPPh 2 , to obtain the novel bis‐phosphine β‐diketimine ligand 1 (PNac‐H).…”

Section: Resultsmentioning

confidence: 99%

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A Phosphine Functionalized β‐Diketimine Ligand for the Synthesis of Manifold Metal Complexes

Zovko

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Schoo

et al. 2020

Chemistry A European J

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Ab is(diphenyl)-phosphine functionalized b-diketimine (PNac-H) was synthesizeda saflexible ligand for transition metal complexes.T he newly designed ligand features symmetrically placed phosphine moieties around a b-diketimine unit, forming aP NNP-type pocket. Due to the hard and soft donora toms (N vs. P) the ligand can stabilize various coordination polyhedra.Acomplete series rangingf rom coordination numbers2to 6w as realized. Linear,t rigonal planar,s quare planar,t etrahedral, square pyramidal,a nd octahedral coordination arrangements containing the PNacligand around the metal centerw ere observed by using suitable metal sources. Hereby, PNac-H or its anion PNac À acts as mono-, bi-and tetradendate ligand. Such ab road flexibility is unusualf or ar igid tetradentate system.T he structural motifs were realized by treatment of PNac-H with as eries of late transitionm etal precursors, for example, silver,g old, nickel, copper, platinum, and rhodium. The new complexes have been fully characterizedb ys ingle crystal X-ray diffraction, NMR,I R, UV/Vis spectroscopy,m ass spectrometry as well as elemental analysis. Additionally,s elected complexes were investigated regarding their photophysical properties. Thus,P Nac-H provedt ob ea ni deal ligand platform for the selectivec oordination and stabilization of variousm etal ions in diversepolyhedra and oxidation states. sis [8, 19-23] as well as the activation of small molecules. [13, 24-26] In this regard, b-diketiminate ligandsh ave been proven capable of supporting metal ions in an umber of oxidation states as well as chemical environments. [27] Especially,t he stabilization of sub-valent andu ncommon oxidation states,f or example, Fe I , [26] Al I , [24, 27, 28] Ga I , [27] Si II , [29] Ge I , [30] and Mg I species, [31, 32] has been an achievement of supporting b-diketiminatel igand systems. Hereby,t he scaffold can be easily modified by varying the corresponding N-substituents,w hicha re adjustable regarding their steric demand, electronic properties as well as the introductiono fa dditional functionalities. [15] Thiso ffers ah igh degreeo fc ontrol for task-specific adjustments, for example, the kinetic stabilization of sub-valent and reactive metal species via sterically demanding substituents, [31, 33, 34] or an enhanced reactivity of the resulting metal complexes. [35, 36] In general,ab-diketiminate ligand provides am onoanionic, bidentate support for metal ions, [15] yet the introduction of additional heteroatom donor sites to the b-diketiminate scaffold allowst he extension to more complex coordination motifs,a higherd egree of metal stabilization as wella st he potential formation of heterobimetallicc omplexes.H erein, the design of the ligand plays ac rucial role in promoting or enforcingspecific arrangements. The introduction of additional side groups to a b-diketimines ystemh as already been investigatedapplying O-donora nd S-donorf unctionalities (Figure1), enabling the formation of multidentate ONNO and SNNS pockets, respectively.T hese bifunctionall ...

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Section: Resultsmentioning

confidence: 99%

“…[Au(tht) 2 [ClO 4 ], [AuC 6 F 5 (tht)], [PtCl 2 (dmso) 2 ] and FNac‐H were prepared according to literature procedures. [AgBF 4 ] (99 %), NaOMe (95 %) and n BuLi (2.5 m in hexane) were purchased from Sigma–Aldrich.…”

Section: Methodsmentioning

confidence: 99%

A Phosphine Functionalized β‐Diketimine Ligand for the Synthesis of Manifold Metal Complexes

Zovko

Bestgen

Schoo

et al. 2020

Chemistry A European J

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“…These results were in agreement with those obtained from the ethylene homopolymerization based on the electronically exible property and electron withdrawing conjugated effect consisting of uorine (F), phenyl ring, imine and titanium(IV) species. [41][42][43][44] Therefore, there was a reason to believe that the (Fsalalen)TiCl 2 /MAO catalyst revealed stronger thermal stability and better catalytic performance for coordination copolymerization of ethylene with 1-octene than (H-salalen)TiCl 2 catalyst.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of ultrahigh-molecular-weight ethylene/1-octene copolymers with salalen titanium(iv) complexes activated by methyaluminoxane

et al. 2022

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“…2,4‐Pentanedione, aniline, 2,6‐difluoroaniline, 2,6‐dichloroaniline were purchased from Energy Chemical (Shanghai), and used as received. Rare‐earth metal tris(alkyl)s, β‐diketiminate ligands (C 6 H 5 )NHC(Me)=CHC(Me)=N(C 6 H 5 ) (HL H ), (2,6‐F 2 C 6 H 3 )NHC(Me)=CHC(Me)=N(2,6‐F 2 C 6 H 3 ) (HL F ) and (2,6‐Cl 2 C 6 H 3 )NHC(Me)=CHC(Me)=N(2,6‐Cl 2 C 6 H 3 ) (HL Cl ) were synthesized according to literatures. NMR ( 1 H, 13 C) spectra were recorded on a Bruker Ascend 500 spectrometer at 25 °C and referenced internally to residual solvent resonances (C 6 D 6 : 7.16 ppm for 1 H NMR, 128.06 ppm for 13 C NMR; [D 8 ]THF: 3.58 ppm for 1 H NMR, 67.21 ppm for 13 C NMR.…”

Section: Methodsmentioning

confidence: 99%

β‐Diketiminato Rare‐Earth Metal Complexes: The Influence of Monoatomic Substituents in the N‐aryl Moieties on Structures and Properties

Zhuang

Mou

et al. 2020

Zeitschrift anorg allge chemie

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Treatment of β‐diketiminate ligands bearing different N‐aryl monoatomic substituents [HLH = (C6H5)N = C(Me)CH=C(Me)NH(C6H5), HLF = (2,6‐F2C6H3)N=C(Me)CH=C(Me)NH(2,6‐F2C6H3), and HLCl = (2,6‐Cl2C6H3)N=C(Me)CH=C(Me)NH(2,6‐Cl2C6H3)] with Ln(CH2SiMe3)3(THF)2 (Ln = Y and Lu) afforded a variety of β‐diketiminato rare‐earth metal complexes depending on substituents, namely, phenyl ring C–H bond activated complexes (L')(LH)Lu(THF) (1b, L' = (C6H4)N = C(Me)CH=C(Me)N(C6H5)), six‐coordinate homoleptic complexes (LH)3Ln [Ln = Y (1aa), Lu (1bb)], five‐coordinate monoalkyl complexes (LF)2Ln(CH2SiMe3) [Ln = Y (2a), Lu (2b)], and four‐coordinate dialkyl complexes (LCl)Ln(CH2SiMe3)2 [Ln = Y (3a), Lu (3b)]. All these complexes were characterized with NMR spectroscopy, and lutetium complexes 1b, 1bb and 3b were structurally validated by single‐crystal X‐ray diffraction analysis. Moreover, dialkyl complexes 3 promoted the polymerization of 2‐vinylpyridine (2‐VP) to produce atactic poly(2‐vinylpyridine) (P2VP) with quantitative yield. On activation with an equimolar amount of [Ph3C][B(C6F5)4], complexes 3 afforded highly isotactic P2VP with an mm value up to 94 %. Both 1H NMR spectrum and MALDI‐TOF mass analysis of an oligomer indicate that the polymerization was initiated by coordination insertion of 2‐VP into the Y‐CH2SiMe3 bond.

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β-diiminato titanium complexes with varying fluorine substitution patterns on the N-aryl moiety: probing the effect of ligand substitution on ethylene polymerization

Cited by 16 publications

References 51 publications

A Phosphine Functionalized β‐Diketimine Ligand for the Synthesis of Manifold Metal Complexes

A Phosphine Functionalized β‐Diketimine Ligand for the Synthesis of Manifold Metal Complexes

Synthesis of ultrahigh-molecular-weight ethylene/1-octene copolymers with salalen titanium(iv) complexes activated by methyaluminoxane

β‐Diketiminato Rare‐Earth Metal Complexes: The Influence of Monoatomic Substituents in the N‐aryl Moieties on Structures and Properties

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