Selective Reductions of <i>N</i>,<i>N</i>‐Bis{chloro(aryl)‐phosphino}‐amines Yielding Three‐, Five‐, Six‐, and Eight‐Membered Cyclic Azaphosphanes

Höhne, Martha; Joksch, Markus; Konieczny, Katharina; Müller, Bernd; Spannenberg, Anke; Peulecke, Normen; Rosenthal, Uwe

doi:10.1002/chem.201605836

Cited by 11 publications

(9 citation statements)

References 57 publications

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“…The molecular structures of 1 , 4 , and 5 have been obtained and discussed previously . Neither the increase of the steric demand at the P atoms or the insertion of space‐filling substituents at the N center led to a smaller P−N−P angle compared to that of 1 .…”

Section: Resultsmentioning

confidence: 94%

“…Thus the reaction temperature could be decreased dramatically from 140 °C for 1 without solvent down to 60 °C for 2 and 3 in DMF, and it was possible to isolate the products in moderate yields. To investigate the effect of varying the surrounding at the N atom, compound 5 was prepared as described by Rosenthal et al …”

Section: Resultsmentioning

confidence: 99%

“…Synthesis of C 12 H 12 Cl 2 NP 2 (1) : The synthesis was performed according to the method of Jefferson et al . For description and characterization see Rosenthal et al …”

Section: Methodsmentioning

confidence: 99%

“…Synthesis of C 19 H 25 Cl 2 NP 2 (4/4*) : For synthesis and characterization see Rosenthal et al . Compound 4 * is the crude product before halogen exchange with ZnCl 2 .…”

Section: Methodsmentioning

confidence: 99%

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Chromium‐Catalyzed Highly Selective Oligomerization of Ethene to 1‐Hexene with N,N‐Bis[chloro(aryl)phosphino]amine Ligands

et al. 2017

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Different N,N‐bis[chloro(aryl)phosphino]amines were synthesized and characterized. The synthesized compounds were tested as ligands in the Cr‐catalyzed oligomerization of ethene. The effect of the successive increase of the steric bulk either at one of the P substituents or at the N center on the product distribution of the oligomerization reaction was examined. We found a highly active and selective trimerization system with purities of the hexene fraction up to 99.9 % for 1‐hexene. Furthermore, we suppose an in situ methylation of the chlorinated ligands into the corresponding N,N‐bis[methyl(aryl)phosphino]amines.

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Section: Resultsmentioning

confidence: 94%

Section: Resultsmentioning

confidence: 99%

“…Synthesis of C 12 H 12 Cl 2 NP 2 (1) : The synthesis was performed according to the method of Jefferson et al . For description and characterization see Rosenthal et al …”

Section: Methodsmentioning

confidence: 99%

“…Synthesis of C 19 H 25 Cl 2 NP 2 (4/4*) : For synthesis and characterization see Rosenthal et al . Compound 4 * is the crude product before halogen exchange with ZnCl 2 .…”

Section: Methodsmentioning

confidence: 99%

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Chromium‐Catalyzed Highly Selective Oligomerization of Ethene to 1‐Hexene with N,N‐Bis[chloro(aryl)phosphino]amine Ligands

et al. 2017

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“…In earlier work we could demonstrate the unusual behavior of the hexahydro‐1,4‐diaza‐2,3,5,6‐tetraphosphorine against group (VI) transition metal carbonyls. Besides the ability to form mono‐ and dinuclear metal complexes (Scheme , A and B ) we observed different kinds of selective P–P bond breakings. Thermal stress can provoke the homolytic cleavage of one P–P bond .…”

Section: Methodsmentioning

confidence: 93%

A Mixed Valent Trinuclear Nickel Complex

Höhne

Müller

Peulecke

et al. 2018

Zeitschrift anorg allge chemie

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The reaction of Ni(PPh 3 ) 2 Cl 2 with hexahydro-1,4-diaza-2,3,5,6-tetraphosphorine in toluene leads to a trinuclear mixed valent nickel complex. Crystal structure analysis confirms three nickel atoms which are connected via two bridging chain-like PNPPNP ligands.In this work, we report the synthesis and characterization of a new trinuclear nickel complex from the reaction of Ni(PPh 3 ) 2 Cl 2 and the newly synthesized PN containing sixmembered ring compound 1 (hexahydro-1,4-diaza-2,3,5,6-tetraphosphorine). The unusual electronic characteristic of this complex is discussed.In earlier work we could demonstrate the unusual behavior of the hexahydro-1,4-diaza-2,3,5,6-tetraphosphorine against group (VI) transition metal carbonyls. Besides the ability to form mono-and dinuclear metal complexes (Scheme 1, A and B) [1] we observed different kinds of selective P-P bond breakings. Thermal stress can provoke the homolytic cleavage of one P-P bond. [2] Presumably, the formation of intermediary phosphinyl radicals led to a dinuclear phosphido bridged tricarbonyl chromium complex (Scheme 1, C). [2] Moreover a metal mediated, highly selective insertion of nitriles into one PP bond of the hexahydro-1,4-diaza-2,3,5,6-tetraphosphorine was presented (Scheme 1, D). The interaction with the metal complex Cr(CO) 3 (MeCN) 3 activates the originally non-polarized symmetrical PP bond of the hexahydro-1,4-diaza-2,3,5,6-tetraphosphorine and allows the insertion of different nitriles, which led to a ring expansion of the coordinating ligand [2] (Scheme 1). Attempts to coordinate the cyclic ligand 1 to nickel precursors led to further unexpected results.The addition of the hexahydro-1,4-diaza-2,3,5,6-tetraphosphorine (1) to a dark blue solution of Ni(PPh 3 )Cl 2 in toluene led to a color change to red brown. The 31 P NMR spectroscopic reaction monitoring showed the release of PPh 3 , which could be separated by extraction with n-pentane. Since no product signal could be detected we assumed the formation of a paramagnetic nickel complex. First the isolation of a very small amount of red crystals allowed the identification of the product by single-crystal X-ray diffraction to be a trinuclear nickel complex (2) (Scheme 2, Figure 1).

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PNPN‐H in Comparison to other PNP, PNPN and NPNPN Ligands for the Chromium Catalyzed Selective Ethylene Oligomerization

Rosenthal

2019

ChemCatChem

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Many examples exist for the chromium catalyzed selective ethylene oligomerization in which the influence of ligands is essential for the formation of products. Regarding the tri‐ and tetramerization to 1‐hexene or 1‐octene mostly PNP ligands are responsible for the tetra‐ and some of such modified ligands for the trimerization. A very special case in these reactions are PNPN−H ligands, showing in most cases highly selective trimerization of ethylene to 1‐hexene. In this review all existing published information about these PNPN−H ligands is accumulated and compared to some other related PNP, PNPN and NPNPN ligands in the chromium catalyzed selective ethylene oligomerization with respect to the switch from tetra‐ to trimerization and back by different substituent pattern of PNP ligand. Mechanistic information and arguments are collected to explain the switch from tetra‐ to trimerization and back by substitution of functional groups in classical PNP to PNPN−H ligands as a result of mono‐ and dinuclear catalytic species.

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Selective Reductions of N,N‐Bis{chloro(aryl)‐phosphino}‐amines Yielding Three‐, Five‐, Six‐, and Eight‐Membered Cyclic Azaphosphanes

Cited by 11 publications

References 57 publications

Chromium‐Catalyzed Highly Selective Oligomerization of Ethene to 1‐Hexene with N,N‐Bis[chloro(aryl)phosphino]amine Ligands

Chromium‐Catalyzed Highly Selective Oligomerization of Ethene to 1‐Hexene with N,N‐Bis[chloro(aryl)phosphino]amine Ligands

A Mixed Valent Trinuclear Nickel Complex

PNPN‐H in Comparison to other PNP, PNPN and NPNPN Ligands for the Chromium Catalyzed Selective Ethylene Oligomerization

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