Organo-aluminum, zinc and magnesium derivatives of the imidotris(amido)phosphate Me3SiNP(NHtBu)3

Robertson, Stuart D.; Chivers, Tristram; Konu, Jari

doi:10.1016/j.jorganchem.2007.06.064

Cited by 13 publications

(10 citation statements)

References 21 publications

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“…Similar to 4 a magnesium complex containing two amidophosphine ligands is known in the literature. Chivers et al published the compound [Mg-{(N t Bu)(NSiMe 3 )P(NH t Bu) 2 } 2 ], which has a quite similar backbone compared to Bauer’s molecule. Chiver’s complex has a Mg−N t Bu bond (2.059(2) Å) that is ca.…”

Section: Resultsmentioning

confidence: 99%

Metalation and Transmetalation Studies on Ph₂PN(ⁱPr)P(Ph)N(ⁱPr)H for Selective Ethene Trimerization to 1-Hexene

et al. 2010

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Different organometallic compounds of the new aminodiphosphinoamine ligand Ph2PN(iPr)P(Ph)N(iPr)-H (1) are reported that are relevant model complexes for the selective ethene trimerization system consisting of ligand 1, CrCl3(THF)3, and Et3Al that produces 1-hexene in more than 90% yield and high purity. The lithiation of 1 by n-BuLi in the presence of tetramethylethylenediamine (tmeda) yields the mononuclear compound Ph2PN(iPr)P(Ph)N(iPr)-][Li(tmeda)] (2). Without using tmeda the dinuclear species [Ph2N(iPr)P(Ph)N(iPr)-Li]2 (3) was obtained. By addition of a Grignard reagent to the ligand solution the bis(aminodiphosphinoamide)magnesium complex [Ph2PN(iPr)P(Ph)N(iPr)-]2Mg (4) could be isolated. Reaction of Li[CpCrCl3] with 3 leads to the formation of the model compound CpCrCl[-N(iPr)P(Ph)N(iPr)PPh2] (5), which can be alkylated with Na[Et4Al] to form the corresponding ethyl compound CpCrEt[-N(iPr)P(Ph)N(iPr)PPh2] (7). In THF the formation of EtCrCl2(THF)3 (8) directly from the reaction of CrCl3[Ph2PN(iPr)P(Ph)N(iPr)-H](THF) (6) with Et3Al could be observed. The organometallic chemistry of 1 gives hints on possible species and activation mechanisms in the catalysis, which have to be considered for a better understanding of the catalytic system.

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Section: Resultsmentioning

confidence: 99%

Metalation and Transmetalation Studies on Ph₂PN(ⁱPr)P(Ph)N(ⁱPr)H for Selective Ethene Trimerization to 1-Hexene

et al. 2010

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“…121 Reactions of {( t BuHN) 3 PNSiMe 3 with n Bu 2 Mg has yielded the monodeprotonated complex [Mg{(N t Bu)(NSiMe 3 )P(NHBu) 2 } 2 ]. 122 The unusual Mg 4 N 4 cubane imide complexes [(ArNMg Á dioxane) 4 Á 3(dioxane)] and [(ArNMg Á THF) 4 ] (Ar = 2,4,6-Cl 3 C 6 H 2 ) have been prepared by the equimolar reaction of n Bu 2 Mg with the primary amine. 123 The coordination chemistry bis-[2-(3,5-dimethyl-1-pyrazolyl)ethyl]amine (LH) with n Bu 2 Mg and monoalkyl magnesium halides has been studied.…”

Section: Group 15 Donorsmentioning

confidence: 99%

Alkali and alkaline earth metals

Hill

2008

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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The aim of this chapter is to reflect major advances in the coordination and organometallic chemistry of the alkali and alkaline earth elements that appeared in peer-reviewed journals throughout 2007. These self-imposed limitations necessarily result in the omission of a great number of noteworthy advances in related fields rooted in either solid-state, materials or theoretical chemistry. The author apologises in advance, therefore, that not all published work can be afforded the same depth of coverage. HighlightsThe undoubted highlight of 2007 occurred toward the end of the year with the report by Jones and Stasch of the first stable magnesium(I) compounds containing a Mg-Mg bond. Other highlights include the first magnesium boryls and the continued growth of the fundamental and applied chemistry of calcium coordination complexes.

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“…Traditional routes to access these anions involve the deprotonation reaction of amido P(V) precursors such as [(RNH) 3 P=E] (E=NR, O, S or Se) in the anhydrous aprotic medium. Strong organometallic reagents that contain main group metal ions such as Li + , Mg 2+ , Zn 2+ and Al 3+ and reactive organyls like alkyls, aryls and silylamides were used as the typical deprotonating agents . The imido‐P(V) anions were isolated as their corresponding metal complexes that exhibit interesting cluster and cage‐like geometries in several instances.…”

Section: Introductionmentioning

confidence: 99%

Chloro‐Bridged Hexanuclear Pd(II) Clusters Supported by cis‐Blocking Tris(imido)phosphate Trianions

et al. 2017

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Transition metal complexes derived from anionic polyimido ligands are very limited in the literature. Here we describe the deprotonation of alkyl substituted phosphoric triamides with bis(benzonitrile)palladium dichloride which results in the formation of chloro-bridged hexanuclear palladium(II) clusters of formula {Pd 3 [(NR) 3 PO](Cl) 3 } 2 in octahedral and prismatic geometries. These clusters consist of two trinuclear Pd 3 -motifs, each cis-protected by a tris(alkylimido)phosphate trianion, which are linked together by six m 2 -Cl bridges. A staggered arrangement of the two imido-Pd 3 units results in the formation of octahedral clusters (R = i Bu, n Bu, c Hex, i Pr and n Pr), while an eclipsed conformation (R = t Bu) gives rise to a prismatic cluster. A similar prismatic configuration was obtained for the mixedbridged clusters {Pd 3 [(NR) 3 PO](OAc) 2 (Cl)} 2 (R = c Hex and i Pr), formed in the reaction involving the corresponding phosphoric triamide, Pd(OAc) 2 and Pd(PhCN) 2 Cl 2 . The reaction of an octahedral cluster {Pd 3 [(N n Pr) 3 PO](Cl) 3 } 2 with 1,1'-ferrocene dicarboxylic acid (FDCÀH) gave the prismatic cluster {Pd 3 [(N n Pr) 3 PO](FDC)(Cl)} 2 which again consists of a mixed-bridged environment with FDC and Cl À linkers. Further, treatment of the octahedral {Pd 3 [(N n Pr) 3 PO](Cl) 3 } 2 cluster with i PrNH 2 , a stronger nucleophile, leads to its symmetric cleavage and forms the trinuclear cluster {Pd 3 [(NR) 3 PO]Cl 3 (R'NH 2 ) 3 }. We have also shown the catalytic activity of some of these Pd(II) complexes in the Suzuki reactions in both organic and aqueous phase conditions which suggest that all these imido-Pd(II) clusters are still suitable for catalytic reactions.

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Organo-aluminum, zinc and magnesium derivatives of the imidotris(amido)phosphate Me3SiNP(NHtBu)3

Cited by 13 publications

References 21 publications

Metalation and Transmetalation Studies on Ph₂PN(ⁱPr)P(Ph)N(ⁱPr)H for Selective Ethene Trimerization to 1-Hexene

Metalation and Transmetalation Studies on Ph₂PN(ⁱPr)P(Ph)N(ⁱPr)H for Selective Ethene Trimerization to 1-Hexene

Alkali and alkaline earth metals

Chloro‐Bridged Hexanuclear Pd(II) Clusters Supported by cis‐Blocking Tris(imido)phosphate Trianions

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Organo-aluminum, zinc and magnesium derivatives of the imidotris(amido)phosphate Me3SiNP(NHtBu)3

Cited by 13 publications

References 21 publications

Metalation and Transmetalation Studies on Ph2PN(iPr)P(Ph)N(iPr)H for Selective Ethene Trimerization to 1-Hexene

Metalation and Transmetalation Studies on Ph2PN(iPr)P(Ph)N(iPr)H for Selective Ethene Trimerization to 1-Hexene

Alkali and alkaline earth metals

Chloro‐Bridged Hexanuclear Pd(II) Clusters Supported by cis‐Blocking Tris(imido)phosphate Trianions

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Metalation and Transmetalation Studies on Ph₂PN(ⁱPr)P(Ph)N(ⁱPr)H for Selective Ethene Trimerization to 1-Hexene

Metalation and Transmetalation Studies on Ph₂PN(ⁱPr)P(Ph)N(ⁱPr)H for Selective Ethene Trimerization to 1-Hexene