Neuartige Reaktionen von Phosphaalkinen in der Koordinationssphäre vontert-Butylimidovanadium(V)-Komplexen: einfache Synthese von 3-Aza-1,2,4,6-tetraphosphaquadricyclanen und 1,3,5-Triphosphabenzolen

Tabellion, Frank; Nachbauer, Anja; Leininger, Stefan; Peters, Christoph; Regitz, Manfred; Preuß, Fritz

doi:10.1002/(sici)1521-3757(19980504)110:9<1318::aid-ange1318>3.0.co;2-l

“…Nucleus‐Independent Chemical Shift (NICS) calculations suggest that the ring is aromatic (NICS(0)=−5.41 ppm; NICS(1)=−7.86 ppm; NICSZZ(0)=−12.49 ppm; NICSZZ(1)=−20.58 ppm) with six π electrons, consistent with the C 3 P 3 3− ring being isolobal to benzene. Compared to 2,4,6‐tris( tert ‐butyl)‐1,3,5‐triphosphabenzene, [22] 5 has smaller P−C−P bond angles (XRD 124.1(4)°, Calcd. 124.8°; t Bu 3 C 3 P 3 : XRD 130.3(3)°, Calcd.…”

Section: Resultsmentioning

confidence: 99%

“…Phosphaalkynes are phosphorus‐containing heavy analogues of nitriles [19] . As with nitriles, the oligomerization of phosphaalkynes is well studied, and can be achieved both stoichiometrically and catalytically using transition metal complexes [20–28] . The cyaphide ion, CP − , is the heavier analogue of cyanide, and also capable of bonding to metal centers [29] .…”

Section: Introductionmentioning

confidence: 99%

Metal‐Mediated Oligomerization Reactions of the Cyaphide Anion

Yang

¹

,

Wilson

²

,

Goicoechea

³

2023

View full text Add to dashboard Cite

The cyaphide anion, CP−, is shown to undergo three distinct oligomerization reactions in the coordination sphere of metals. Reductive coupling of Au(IDipp)(CP) (IDipp=1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene) by Sm(Cp*)2(OEt2) (Cp*=1,2,3,4,5‐pentamethylcyclopentadienyl), was found to afford a tetra‐metallic complex containing a 2,3‐diphosphabutadiene‐1,1,4,4‐tetraide fragment. By contrast, non‐reductive dimerization of Ni(SIDipp)(Cp)(CP) (SIDipp=1,3‐bis(2,6‐diisopropylphenyl)‐imidazolidin‐2‐ylidene; Cp=cyclopentadienyl), gives rise to an asymmetric bimetallic complex containing a 1,3‐diphosphacyclobutadiene‐2,4‐diide moiety. Spontaneous trimerization of Sc(Cp*)2(CP) results in the formation of a trimetallic complex containing a 1,3,5‐triphosphabenzene‐2,4,6‐triide fragment. These transformations show that while cyaphido transition metal complexes can be readily accessed using metathesis reactions, many such species are unstable to further oligomerization processes.

show abstract

“…Phosphaalkynes are phosphorus‐containing heavy analogues of nitriles [19] . As with nitriles, the oligomerization of phosphaalkynes is well studied, and can be achieved both stoichiometrically and catalytically using transition metal complexes [20–28] . The cyaphide ion, CP − , is the heavier analogue of cyanide, and also capable of bonding to metal centers [29] .…”

Section: Introductionmentioning

confidence: 99%

Metal‐Mediated Oligomerization Reactions of the Cyaphide Anion

Yang

¹

,

Wilson

²

,

Goicoechea

³

2023

Angewandte Chemie

0

View full text Add to dashboard Cite

The cyaphide anion, CP−, is shown to undergo three distinct oligomerization reactions in the coordination sphere of metals. Reductive coupling of Au(IDipp)(CP) (IDipp=1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene) by Sm(Cp*)2(OEt2) (Cp*=1,2,3,4,5‐pentamethylcyclopentadienyl), was found to afford a tetra‐metallic complex containing a 2,3‐diphosphabutadiene‐1,1,4,4‐tetraide fragment. By contrast, non‐reductive dimerization of Ni(SIDipp)(Cp)(CP) (SIDipp=1,3‐bis(2,6‐diisopropylphenyl)‐imidazolidin‐2‐ylidene; Cp=cyclopentadienyl), gives rise to an asymmetric bimetallic complex containing a 1,3‐diphosphacyclobutadiene‐2,4‐diide moiety. Spontaneous trimerization of Sc(Cp*)2(CP) results in the formation of a trimetallic complex containing a 1,3,5‐triphosphabenzene‐2,4,6‐triide fragment. These transformations show that while cyaphido transition metal complexes can be readily accessed using metathesis reactions, many such species are unstable to further oligomerization processes.

show abstract

Novel Tetraphosphabarrelene and -semibullvalene Derivatives by Reactions of 2,4,6-Tri-tert-butyl-1,3,5-triphosphabenzene with Phosphaalkynes⋆

Binger¹,

Stutzmann

²

,

Bruckmann

³

et al. 1998

Eur. J. Inorg. Chem.

View full text Add to dashboard Cite

2,4,6‐Tri‐tert‐butyl‐1,3,5‐triphosphabenzene 4 reacts with phosphaalkynes P≡C–R [R = tBu (5a), tPen (5b)] at room temperature in a formal [4 + 2] cycloaddition to yield the corresponding 1,3,5,7‐tetraphosphabarrelene derivatives 8a and 8b, respectively. The analogous reaction of 4 with the aminophosphaethyne P≡C–N(iPr)2 (9) unexpectedly leads to the 1,3,4,7‐tetraphosphasemibullvalene derivative 10 as the only product. The single‐crystal X‐ray analysis of 10 exhibits a diphosphirane unit with a very long PP distance of 2.274(1) Å together with a large extension of the PCP angle in the three‐membered ring to 75.3(1)°.

show abstract

Neuartige Reaktionen von Phosphaalkinen in der Koordinationssphäre vontert-Butylimidovanadium(V)-Komplexen: einfache Synthese von 3-Aza-1,2,4,6-tetraphosphaquadricyclanen und 1,3,5-Triphosphabenzolen

Cited by 39 publications

References 24 publications

Metal‐Mediated Oligomerization Reactions of the Cyaphide Anion

Metal‐Mediated Oligomerization Reactions of the Cyaphide Anion

Metal‐Mediated Oligomerization Reactions of the Cyaphide Anion

Novel Tetraphosphabarrelene and -semibullvalene Derivatives by Reactions of 2,4,6-Tri-tert-butyl-1,3,5-triphosphabenzene with Phosphaalkynes⋆

Contact Info

Product

Resources

About