Triple-Bond Reactivity of Diphosphorus Molecules

  title={Triple-Bond Reactivity of Diphosphorus Molecules},
  author={Nicholas A. Piro and Joshua S. Figueroa and Jessica T McKellar and Christopher C. Cummins},
  pages={1276 - 1279}
We report a mild method for generating the diphosphorus molecule or its synthetic equivalent in homogeneous solution; the P2 allotrope of the element phosphorus is normally obtained only under extreme conditions (for example, from P4 at 1100 kelvin). Diphosphorus is extruded from a niobium complex designed for this purpose and can be trapped efficiently by two equivalents of an organic diene to produce an organodiphosphorus compound. Diphosphorus stabilized by coordination to tungsten… 
The chemistry of phosphirane-substituted phosphinidene complexes.
Thermolysis of the 1,1'-biphosphirane pentacarbonylmetal complex offers access to 3,4-dihydro-1,2-diphosphete and diphosphorus (P2) intermediates and DFT calculations predict that further transformations proceed via a transient phosphiranylphosphinidene complex.
Photochemical incorporation of diphosphorus units into organic molecules.
A niobium-based method for thermal transfer of P2 to 1,3dienes to make the interesting class of bior tetracyclic P2R4 molecules readily available for detailed scrutiny is discovered and a simple one-step procedure is discovered, reported herein.
A stable phosphanyl phosphaketene and its reactivity.
Sodium phosphaethynolate reacts with the bulky P-chloro-diazaphosphole yielding a phosphanyl phosphaketene, which is stable for weeks under an inert atmosphere in the solid state and dimerization/CO loss were computed with various DFT methods which allowed us to understand the reaction mechanisms.
Transition Metal Functionalization of P4 Using a Diarylgermylene Anchor.
Lewis acidic transition metal moieties M(CO)5 and AuCl react with P4 derivatized with a low valent germanium compound, and bis-functionalized products can be formed; however the monosubstituted derivatives are found to be more stable, and the decomposition can be monitored by 31P{1H} NMR spectroscopy.
Dipnictogen f-Element Chemistry: A Diphosphorus Uranium Complex.
The synthesis of a side-on bound diphosphorus complex of uranium(IV) using a 7λ3-(dimethylamino)phosphadibenzonorbornadiene-mediated P atom transfer approach is reported, suggesting in situ generation of transient, reactive phosphido species.
Triple-bond reactivity of an AsP complex intermediate: synthesis stemming from molecular arsenic, As(4).
As(4) activation giving rise to a mu-As(2) diniobium complex, serving in turn as precursor to a terminal arsenide anion complex of niobium, which provides the new AsPNMes* ligand.
Reactivity Studies on a Diazadiphosphapentalene.
It was demonstrated that only one of the phosphorus atoms in 1 behaves as an electron donor for electrophiles and Lewis acids and that UV irradiation induced rearrangement of 1 into another example of another diazadiphosphapentalene.
Functionalization of P4 through Direct P−C Bond Formation
An overview of recent breakthroughs in chlorine‐free conversions of P4 into organophosphorus compounds (OPCs) is provided and the acquired fundamental insights to aid future developments are outlined.
Oxidative Coupling of Terminal Rhenium Pnictide Complexes.
Computational bond analysis suggests best description as {Pn2}0 complexes that are stabilized by donor-acceptor interactions with the metal and a pyrazole ligand.


Activation of P4 and P2 by Transition Metal Complexes at Room Temperature.
Two multinuclear complexes are formed-one with a ReWP2 tetrahedrane framework and 2, whose six atoms Re2 P2 W2 form a plane and in which the P2 ligand of the butterfly complex is converted into two µ-P ligands.
Metal-Mediated Degradation and Reaggregation of White Phosphorus
A critical survey of the coordination chemistry of white phosphorus illustrating the metal-mediated degradation of the P4 tetrahedron is presented. The underlying principles to account for the
A niobaziridine hydride system for white phosphorus or dinitrogen activation and N- or P-atom transfer.
In a fashion analogous to the aforementioned phosphaalkyne synthesis, acid chlorides are transformed upon reaction with the niobium nitride anion into corresponding nitrogen-15 labeled organic nitriles, as the oxoniobium(v) byproduct can be recycled in high yield to the title niobaziridine hydride complex.
Mechanistic Aspects of Diels‐Alder Reactions: A Critical Survey
The question of concerted or consecutive bond formation arises in all types of cycloaddition reactions. Stereochemical investigations and studies of regiospecificity as well as intensive kinetic
Synthesis, Structures, and Kinetics and Mechanism of Decomposition of Terminal Metal Azide Complexes: Isolated Intermediates in the Formation of Imidometal Complexes from Organic Azides
Treatment of Cp2Ta(CH3)(PMe3) (Cp = η5-C5H5) with aryl azides ArN3 (Ar = C6H5, p-CF3C6H4, p-NMe2C6H4) affords rare examples of terminal phenylazido complexes Cp2Ta(CH3)(N3Ar) and free phosphine in ...
Terminal, anionic carbide, nitride, and phosphide transition-metal complexes as synthetic entries to low-coordinate phosphorus derivatives.
Anionic terminal one-atom nitride, phosphide, and carbide complexes are excellent starting materials for the synthesis of ligands containing low-coordinate phosphorus centers in the protecting
Phosphorus: The Carbon Copy: From Organophosphorus to Phospha-organic Chemistry
The Phosphorus-Carbon Analogy: Phospha-organic Chemistry. Phosphinidenes (R-P). Terminal Phosphinidene Complexes [R-P=M]. Phosphaalkynes (RC=P). Phosphaalkenes, R1R2C=PR3. Phosphapolyenes.
An expedient phosphine-catalyzed [4 + 2] annulation: synthesis of highly functionalized tetrahydropyridines.
Mechanistic reasoning for this new annulation has led to an expansion of the reaction scope by employing ethyl 2-(substituted-methyl)-2,3-butadienoates to give Ethyl 2,6-cis-disubst ituted-1-(4-tosyl)-1,2,5, 6-tetrahydro-pyridine-3-carboxylates with high diastereoselectivities.
Phosphaalkynes from acid chlorides via P for O(Cl) metathesis: a recyclable niobium phosphide (P(3-)) reagent that effects C-P triple-bond formation.
Complex 7 provides direct access to 1 upon reduction with magnesium anthracene, thus completing a cycle of element activation, small-molecule generation via metathetical P-atom transfer, and deoxygenative recycling of the final niobium(V) oxo product.