Reactivity with alkylaluminum of a chromium complex of a pyridine-containing PNP ligand: Redox N-P bond cleavage

Ahmed Alzamly; Sandro Gambarotta; Ilia Korobkov

doi:10.1021/om401129w

Reactivity with alkylaluminum of a chromium complex of a pyridine-containing PNP ligand: Redox N-P bond cleavage

Ahmed Alzamly, Sandro Gambarotta, Ilia Korobkov

Research output: Contribution to journal › Article › peer-review

23 Citations (Scopus)

Abstract

The ligand 2,6-[(Ph₂)₂PN]₂C ₅H₃N based on the popular PNP motif has been used to generate the corresponding chromium adduct {2,6-[(Ph₂) ₂PN]₂C₅H₃N}CrCl₃· 2.5THF (1). Its reaction with Et₂AlCl and Cl₂AlEt afforded the two nearly isostructural complexes {2,6-(Ph₂PNH)[(Et ₂ClAl)NPPh₂]C₅H₃N}CrCl(PEtPh ₂)·0.5(toluene) (2) and {2,6-(Ph₂PNH)[(EtCl ₂Al)NPPh₂]C₅H₃N}CrCl(PEtPh ₂)·0.5(toluene) (3). The formation of these two species is the result of a multiple attack of the activator at both the ligand system and the metal center. During the reaction, the two nitrogen atoms lost one phosphine residue each, the metal was reduced, one of the two nitrogens was protonated, and one EtPPh₂ molecule was formed and retained by the metal center. The three complexes characterized in this work display activity for catalytic and nonselective ethylene oligomerization.

Original language	English
Pages (from-to)	1602-1607
Number of pages	6
Journal	Organometallics
Volume	33
Issue number	7
DOIs	https://doi.org/10.1021/om401129w
Publication status	Published - Apr 14 2014
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Reactivity with alkylaluminum of a chromium complex of a pyridine-containing PNP ligand: Redox N-P bond cleavage",

abstract = "The ligand 2,6-[(Ph2)2PN]2C 5H3N based on the popular PNP motif has been used to generate the corresponding chromium adduct {2,6-[(Ph2) 2PN]2C5H3N}CrCl3· 2.5THF (1). Its reaction with Et2AlCl and Cl2AlEt afforded the two nearly isostructural complexes {2,6-(Ph2PNH)[(Et 2ClAl)NPPh2]C5H3N}CrCl(PEtPh 2)·0.5(toluene) (2) and {2,6-(Ph2PNH)[(EtCl 2Al)NPPh2]C5H3N}CrCl(PEtPh 2)·0.5(toluene) (3). The formation of these two species is the result of a multiple attack of the activator at both the ligand system and the metal center. During the reaction, the two nitrogen atoms lost one phosphine residue each, the metal was reduced, one of the two nitrogens was protonated, and one EtPPh2 molecule was formed and retained by the metal center. The three complexes characterized in this work display activity for catalytic and nonselective ethylene oligomerization.",

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doi = "10.1021/om401129w",

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T1 - Reactivity with alkylaluminum of a chromium complex of a pyridine-containing PNP ligand

T2 - Redox N-P bond cleavage

AU - Alzamly, Ahmed

AU - Gambarotta, Sandro

AU - Korobkov, Ilia

PY - 2014/4/14

Y1 - 2014/4/14

N2 - The ligand 2,6-[(Ph2)2PN]2C 5H3N based on the popular PNP motif has been used to generate the corresponding chromium adduct {2,6-[(Ph2) 2PN]2C5H3N}CrCl3· 2.5THF (1). Its reaction with Et2AlCl and Cl2AlEt afforded the two nearly isostructural complexes {2,6-(Ph2PNH)[(Et 2ClAl)NPPh2]C5H3N}CrCl(PEtPh 2)·0.5(toluene) (2) and {2,6-(Ph2PNH)[(EtCl 2Al)NPPh2]C5H3N}CrCl(PEtPh 2)·0.5(toluene) (3). The formation of these two species is the result of a multiple attack of the activator at both the ligand system and the metal center. During the reaction, the two nitrogen atoms lost one phosphine residue each, the metal was reduced, one of the two nitrogens was protonated, and one EtPPh2 molecule was formed and retained by the metal center. The three complexes characterized in this work display activity for catalytic and nonselective ethylene oligomerization.

AB - The ligand 2,6-[(Ph2)2PN]2C 5H3N based on the popular PNP motif has been used to generate the corresponding chromium adduct {2,6-[(Ph2) 2PN]2C5H3N}CrCl3· 2.5THF (1). Its reaction with Et2AlCl and Cl2AlEt afforded the two nearly isostructural complexes {2,6-(Ph2PNH)[(Et 2ClAl)NPPh2]C5H3N}CrCl(PEtPh 2)·0.5(toluene) (2) and {2,6-(Ph2PNH)[(EtCl 2Al)NPPh2]C5H3N}CrCl(PEtPh 2)·0.5(toluene) (3). The formation of these two species is the result of a multiple attack of the activator at both the ligand system and the metal center. During the reaction, the two nitrogen atoms lost one phosphine residue each, the metal was reduced, one of the two nitrogens was protonated, and one EtPPh2 molecule was formed and retained by the metal center. The three complexes characterized in this work display activity for catalytic and nonselective ethylene oligomerization.

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Reactivity with alkylaluminum of a chromium complex of a pyridine-containing PNP ligand: Redox N-P bond cleavage

Abstract

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