Reactions of lithiated diphosphanes R 2 P-P(SiMe 3 )Li· n THF (R = t Bu, i Pr) with [(PNP)TiCl 2 ]. Two different coordination types of phosphanylphosphido ligand to the metal center

Ponikiewski, Łukasz; Ziółkowska, Aleksandra; Zauliczny, Mateusz; Pikies, Jerzy

doi:10.1016/j.poly.2017.08.007

Cited by 10 publications

(3 citation statements)

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“…Close interactions were observed in [(Ar)NC(Me)CHC(Me)P(Trip)(CH 2 tBu)Ti NAr(OEt 2 )], as the related distances were 2.420(8) and 2.456(9) Å. 61 The P1−P2 distance (2.2165(12) Å) is typical for a P−P single bond and is slightly longer than those observed in previously described terminal phosphanylphosphido complexes of titanium ([(PNP)Ti(Cl){η 1 -P(SiMe 3 )-PtBu 2 }] (2.1961(9) Å)), 38 zirconium ([Ind 2 Zr(Cl){η 1 -P-(SiMe 3 )-PtBu 2 }] (2.201(1) Å), 41 and [Cp 2 Zr(Cl){η 1 -P-(SiMe 3 )-PiPr 2 }] (2.187(2) Å)) and hafnium ([Cp 2 Hf(Cl)-{η 1 -P(SiMe 3 )-PiPr 2 }] (2.185(1) Å)). 40 The geometry around P1 and P2 atoms is clearly pyramidal (ΣP1 = 296.72°and ΣP2 = 310.04°).…”

Section: Resultsmentioning

confidence: 89%

“…Our group has studied metathesis reactions of R′R′′P-P(SiMe 3 )Li with transition metal compounds bearing chloride ligands to introduce phosphanylphosphinidene R′R′′P-P and phosphanylphosphido R′R′′P-P(SiMe 3 ) moieties into the product complexes (R′ = t Bu and i Pr; R′′ = t Bu, i Pr, and Ph). Phosphanylphosphido complexes have been obtained for titanium, − iron, hafnium, zirconium, − tungsten, and molybdenum, and phosphanylphosphinidene complexes have been reported for titanium, , zirconium, , tungsten, , molybdenum, and platinum. − Among these complexes, the complexes of titanium, zirconium, and iron were stabilized using a β-diketiminate ligand. The reactivity of the phosphanylphosphinidene complexes of tungsten was investigated by Grubba and co-workers. , Moreover, the reactivities of monophosphorus analogues M–P and P–R are also rarely reported.…”

Section: Introductionmentioning

confidence: 99%

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Solvent Impact on the Diversity of Products in the Reaction of Lithium Diphenylphosphide and a Ti(III) Complex Supported by a tBu₂P–P(SiMe₃) Ligand

et al. 2020

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We present two important trends in the reactivity of the titanium complex [ Me NacNacTi(Cl){η 2 -P(SiMe 3 )-P t Bu 2 }] ( Me NacNac – = [Ar]NC(Me)CHC(Me)N[Ar]; Ar = 2,6- i Pr 2 Ph) with nucleophilic reagents RLi (R = Ph 2 P, t BuO, (Me 3 Si) 2 N, and t Bu 2 N) depending on the reaction medium. Reaction in nonpolar solvent (toluene) leads to three main products: via an autoredox process and nucleophilic substitution at the Ti-atom to afford the Ti(IV) complex [ Me NacNacTi(R){η 2 -P-P t Bu 2 }] ( 1 for R = PPh 2 ), via the elimination of Me 3 SiR to afford Ti(III) complex [ Me NacNacTi(Cl){η 2 -P-P t Bu 2 }] − [Li(12-crown-4) 2 ] + ( 2 ), and via 2e – reduction process to afford new ionic complex [{ArNC(Me)CHC(Me)}Ti=NAr{η 1 -P(SiMe 3 )-P t Bu 2 }] − [Li(12-crown-4) 2 ] + ( 3 ). Quite differently, the complex [ Me NacNacTi(Cl){η 2 -P(SiMe 3 )-P t Bu 2 }] reacts with Ph 2 PLi in THF, unexpectedly yielding two new, four-coordinate Ti(IV) imido complexes 4a [{ArNC(Me)=CHC(H)(Me)-P(P t Bu 2 )}Ti=NAr(Cl)] − [Li(12-crown-4) 2 ] + ·(toluene) 2 and 4b [{ArNC(CH 2 )CH=C(Me)-P(P t Bu 2 )}Ti=NAr(Cl)] − [Li(12-crown-4) 2 ] + ·(Et 2 O). Complex 2 dissolved in THF converts to 4a and 4b . 1 , 2 , 3 , 4a , and 4b were characterized by X-ray diffraction. 1 , 4a , and 4b were also fully characterized by multinuclear NMR spectroscopy.

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Section: Resultsmentioning

confidence: 89%

Section: Introductionmentioning

confidence: 99%

Solvent Impact on the Diversity of Products in the Reaction of Lithium Diphenylphosphide and a Ti(III) Complex Supported by a tBu₂P–P(SiMe₃) Ligand

et al. 2020

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“…These values are in line with literature values for a titanium (III) centre. [78][79][80][81] Figure 2: ORTEP plot of 1. Thermal ellipsoids at 50% probability, hydrogens omitted for clarity.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Reactivity of titanium ‘POCOP’ pincer complexes

Chadwick

Krämer

Webster

2022

Preprint

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The ‘POCOP’ pincer ligand, [2,6-(R2PO)2C6H3], has been attached to titanium in both Ti(III) and Ti(IV) complexes for the first time. Using a lithium-halogen exchange route [2.6-(R2O)2C6H3]Li ([RPOCOP]Li) can be synthesised. Both the iso-propyl and tert-butyl derivatives can be made, but only the latter isolated. These can be reacted with the Ti(III) and Ti(IV) synthons to make [tBuPOCOP]TiCl2 (1), [tBuPOCOP]TiCl3 (2) and {[iPrPOCOP]TiCl2(µ-Cl)}2 (4). In the presence of Ti(IV), THF and [RPOCOP]Li an unprecedented ligand rearrangement occurs. 1 can be derivatised with alkylating agents to make bis-methyl, phenyl and neopentyl complexes. The last of these can activate H2 to make a rare example of a titanium hydride chloride, with the metal pincer fragment staying attached. This opens the door for this archetypical pincer ligand to be used with early transition metals.

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First Copper(I) and Silver(I) Complexes Containing Phosphanylphosphido Ligands

Ziółkowska

Brauer

Ponikiewski

2019

Zeitschrift anorg allge chemie

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Three new complexes with phosphanylphosphido ligands, [Cu 4 {μ 2 -P(SiMe 3 )-PtBu} 4 ] (1), [Ag 4 {μ 2 -P(SiMe 3 )-PtBu 2 } 4 ] (2) and [Cu{η 1 -P(SiMe 3 )-PiPr 2 } 2 ] -[Li(Diglyme) 2 ] + (3) were synthesized and structurally characterized by X-ray diffraction, NMR spectroscopy, and elemental analysis. Complexes 1 and 2 were obtained in the reactions of lithium derivative of diphosphane tBu 2 P-P(SiMe 3 )Li·2.7THF with CuCl and [iBu 3 PAgCl] 4 , respectively. The X-ray diffraction analysis

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Reactions of lithiated diphosphanes R 2 P-P(SiMe 3 )Li· n THF (R = t Bu, i Pr) with [(PNP)TiCl 2 ]. Two different coordination types of phosphanylphosphido ligand to the metal center

Cited by 10 publications

References 54 publications

Solvent Impact on the Diversity of Products in the Reaction of Lithium Diphenylphosphide and a Ti(III) Complex Supported by a tBu₂P–P(SiMe₃) Ligand

Solvent Impact on the Diversity of Products in the Reaction of Lithium Diphenylphosphide and a Ti(III) Complex Supported by a tBu₂P–P(SiMe₃) Ligand

Synthesis and Reactivity of titanium ‘POCOP’ pincer complexes

First Copper(I) and Silver(I) Complexes Containing Phosphanylphosphido Ligands

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Reactions of lithiated diphosphanes R 2 P-P(SiMe 3 )Li· n THF (R = t Bu, i Pr) with [(PNP)TiCl 2 ]. Two different coordination types of phosphanylphosphido ligand to the metal center

Cited by 10 publications

References 54 publications

Solvent Impact on the Diversity of Products in the Reaction of Lithium Diphenylphosphide and a Ti(III) Complex Supported by a tBu2P–P(SiMe3) Ligand

Solvent Impact on the Diversity of Products in the Reaction of Lithium Diphenylphosphide and a Ti(III) Complex Supported by a tBu2P–P(SiMe3) Ligand

Synthesis and Reactivity of titanium ‘POCOP’ pincer complexes

First Copper(I) and Silver(I) Complexes Containing Phosphanylphosphido Ligands

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Product

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Solvent Impact on the Diversity of Products in the Reaction of Lithium Diphenylphosphide and a Ti(III) Complex Supported by a tBu₂P–P(SiMe₃) Ligand

Solvent Impact on the Diversity of Products in the Reaction of Lithium Diphenylphosphide and a Ti(III) Complex Supported by a tBu₂P–P(SiMe₃) Ligand