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

Hill, Michael S.; Hitchcock, Peter B.; Karagouni, Sophia M.A

doi:10.1016/j.jorganchem.2003.11.030

Cited by 39 publications

(48 citation statements)

References 65 publications

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“…It is of interest to note that the bridging carbon in R 2 CK 2 and R 2 CRb 2 is tetrahedrally surrounded by the P substituents and the metals. This contrasts with theoretical predictions for the dimers [H 2 CM 2 ] 2 (M = Li, K, Rb, Cs) which are build up from two H 2 CM 2 molecules with a planar tetracoordinate carbon atom (19) [34]; the carbon in [H 2 CNa 2 ] 2 bridges four Na + ions with roughly equal distances [33]. This disagreement between theoretical models and the experimentally found K 4 -and Rb 4 -clusters is likely caused by the effect of the two chelating iminophosphorane arms.…”

Section: Homometallic Methandiide Complexescontrasting

confidence: 84%

“…the metal does not bind to the bridging carbon but is chelated by the iminophosphorano arms (similar to 10). Only in a few cases very weak carbon-metal interaction, indicated by a long bond distance, is found [19,22,23].…”

Section: Homometallic Methandiide Complexesmentioning

confidence: 97%

“…Treatment of a bis(iminophosphorane)methane precursor with one equivalent of an alkali metal base gave the expected methanide complexes for a variety of alkali metals (Li, Na, K) and iminosubstituents: R = Me 3 Si, mesityl, DIPP (2, 6-diisopropylphenyl) or P(O)(OPh) 2 [18][19][20][21][22][23][24][25]. Crystal structure determinations generally show zwitterionic behaviour, i.e.…”

Section: Homometallic Methandiide Complexesmentioning

confidence: 99%

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Geminal dianions stabilized by phosphonium substituents

Harder

2011

Coordination Chemistry Reviews

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Section: Homometallic Methandiide Complexescontrasting

confidence: 84%

Section: Homometallic Methandiide Complexesmentioning

confidence: 97%

Section: Homometallic Methandiide Complexesmentioning

confidence: 99%

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Geminal dianions stabilized by phosphonium substituents

Harder

2011

Coordination Chemistry Reviews

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“…The P1C13C14O1 atoms (the torsion angle 5.8°) in complex 6 display more deviation from a plane compared with those corresponding ones in complex 3 (the torsion angle 0.9°). Both Al-N and Al-O distances (1.862(4) and 1.749(4) Å, respectively) in complex 6 are shorter than those of complex 3, but still within normal range for a four-coordinate aluminum halide complex [26,28].…”

Section: Synthesis and Characterization Of Compounds 1-6mentioning

confidence: 84%

“…The Al-C distance of average 1.965 Å is normal compared with a range of four-coordinated methyl aluminum complexes [26]. The Al-N distance of 1.938(3) Å is comparable to those of iminophosphorane coordinated aluminum complexes [27][28][29][30]. For example, the Al-N distance is 1.…”

Section: Synthesis and Characterization Of Compounds 1-6mentioning

confidence: 86%

Synthesis of lithium and aluminum complexes supported by [OC(But)CHP(Ph2)=NBut]− ligand and catalysis of [R2Al{OC(But)-CHP(Ph2)=NBut}] (R = Me, Et) and [Me2Al{1-{OC(Ph)CH}-3-R1-5-MeC3HN2}] (R1 = Me, But) in the ring-opening polymerization of ɛ-caprolactone

2010

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A series of lithium and aluminum complexes bearing [OC(Bu t )CHP(Ph 2 )=NBu t ] -ligand were synthesized and characterized. Reaction of Bu t C(O)CH 2 Br with Ph 2 PNHBu t afforded [Ph 2 P(NHBu t )CH 2 C(O)Bu t ] + Br -(1). Treatment of 1 with excess of NaH in THF generated ligand precursor Ph 2 P(CH 2 C(O)Bu t )=NBu t (2). Reaction of 2 with AlR 3 (R = Me, Et) gave N,O-chelate aluminum complexes [R 2 Al{OC(Bu t )CHP(Ph 2 )=NBu t }] (3, R = Me; 4, R = Et). Lithiation of 2 with an equiv. of LiBu n formed lithium complex [Li{OC(Bu t )CHP(Ph 2 )=NBu t }] (5). Reaction of the lithium complex with an equiv. of AlCl 3 yielded [Cl 2 Al{OC(Bu t ) CHP(Ph 2 )=NBu t }] (6). Complex 6 was also obtained by reaction of 3 with an equiv. of AlCl 3 . Compounds 2-6 were characterized by NMR spectroscopy, elemental analysis and single crystal X-ray diffraction techniques (for 2, 3 and 6). Catalysis of complexes 3 and 4 as well as [Me 2 Al{1-{OC(Ph)CH}-3-R 1 -5-MeC 3 HN 2 }] (R 1 = Me, Bu t ) toward the ring-opening polymerization of ε-caprolactone was investigated. N,O-chelate ligands, complex, lithium, aluminum, synthesis, catalysis Citation: Yang D, Cai C F, Wang Z X. Synthesis of lithium and aluminum complexes supported by [OC(Bu t )CHP(Ph 2 )=NBu t ] -ligand and catalysis of [R 2 Al{OC(Bu t ) CHP(Ph 2 )=NBu t }] (R = Me, Et) and [Me 2 Al{1-{OC(Ph)CH} -3-R 1 -5-MeC 3 HN 2 }] (R 1 = Me, Bu t ) in the ring-opening polymerization of ε-caprolactone. Synthetic aliphatic polyesters such as poly(ε-caprolactone) (PCL) and polylactide (PLA) are important materials in biomedical and pharmaceutical applications due to their biodegradable, biocompatible and permeable properties [1-5]. These polymers are usually synthesized by the ring-opening polymerization (ROP) of cyclic esters such as lactones and lactides initiated by metal complexes. The metal-initiated-ROP can enable control of polymer molecular weight and polymer architecture and can yield macromolecular samples with narrow molecular weight distributions [3-8]. Among the catalysts/initiators studied, aluminum complexes have attracted much attention due to their *Corresponding author (email: zxwang@ustc.edu.cn) high activity and selectivity as well as low toxicity of aluminum [9-13]. On the other hand, properties of complexes strongly rely on supporting ligands besides the metal itself. The ligands can tune the properties of the metal center and minimize the aggregation processes and side reactions during the process of polymerization. N,O-Chelate ligands are one of the most often used ligands in aluminum-based catalytic systems. A series of N,O-chelate aluminum complexes such as ketiminate, salicylaldimine, SALAN and SALEN aluminum complexes exhibited excellent catalytic behavior in the ring-opening polymerization of cyclic esters [14-19]. Herein we report synthesis and characterization of lithium and aluminum complexes bearing [OC(Bu t )CHP(Ph 2 )= NBu t ] -ligand and catalysis of [R 2 Al{OC(Bu t )CHP(Ph 2 )=

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Bi‐ and tridentate coordination behaviour of a novel bis(phosphinimino)methanide ligand

Burgert,

Sun,

Hauser

et al. 2024

Chemistry An Asian Journal

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Herein, we report the synthesis of a novel ferrocenyl functionalized bis(phosphinimino)methane ligand (CH2(PPh2NFc)2). Deprotonation of CH2(PPh2NFc)2 with KN(SiMe3)2 gave the dimeric species [K{CH(PPh2NFc)2}]2, which was further reacted with ECl2 (E = Ge, Sn) to yield the tetrylene compounds [{CH(PPh2NFc)2}ECl]. The ligand and the resulting tetrylenes were examined for their redox chemical properties by cyclovoltammetric measurements. Furthermore, the reaction of the tetrylenes [{CH(PPh2NFc)2}ECl] with [AuC6F5(tht)] resulted in the bimetallic complexes [{(AuC6F5)CH(PPh2NFc)2}ECl] with an unusual Au coordination on the ligand backbone.

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

Cited by 39 publications

References 65 publications

Geminal dianions stabilized by phosphonium substituents

Geminal dianions stabilized by phosphonium substituents

Synthesis of lithium and aluminum complexes supported by [OC(But)CHP(Ph2)=NBut]− ligand and catalysis of [R2Al{OC(But)-CHP(Ph2)=NBut}] (R = Me, Et) and [Me2Al{1-{OC(Ph)CH}-3-R1-5-MeC3HN2}] (R1 = Me, But) in the ring-opening polymerization of ɛ-caprolactone

Bi‐ and tridentate coordination behaviour of a novel bis(phosphinimino)methanide ligand

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