C‐Phosphoniophosphaalkenes as Precursors of 1σ4,3σ2‐Diphosphaallenes: Scope and Limitations

Martín, David; Baceiredo, Antoine; Bertrand, Guy

doi:10.1002/ejic.200500014

Cited by 14 publications

(3 citation statements)

References 16 publications

(10 reference statements)

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“…In the case of the diphosphaallenes, charge transfers from a lone pair of one phosphorus atom to a σ antibonding orbital localized on the C-P bond involving the other phosphorus are present, these interactions forcing the P-C-P angle to narrow. This type of interaction is also present for the discussed derivative IV.5 between the lone pair of the λ 3 σ 2 P and an antibonding orbital of σ symmetry on λ 5 σ 3 P-C; the orbitals involved are represented in The data of Table 2 show that the P-C-P angle is as expected highly dependent on the nature of the substituents on the phosphorus atom and of its hybridization [13][14][15][16][17][18]. A very strained angle of 115.05º has been reported for i-Pr 2 NP=C=PPh 2 Ni-Pr 2 [16], a derivative containing dicoordinated trivalent and tetracoordinated pentavalent phosphorus atoms in the PCP backbone.…”

Section: Resultssupporting

confidence: 53%

Theoretical study of structural patterns in CH2OP2 isomers

et al. 2010

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DFT calculations have been performed on the derivatives of formula CH 2 OP 2 to determine their total energy, the relative energy between the isomers and their geometry. Among compounds with a P-C-P linkage, the most stable one is the 2-hydroxy-1,2-diphosphirene II.1, a threemembered heterocycle with a P=C unsaturation. The phosphavinylidene(oxo)phosphorane HP=C=P(O)H IV.5 (which has the same skeleton as the experimentally obtained Mes*P=C=P(O)Mes*) lies 36.30 kcal mol -1 above it. The least stable compounds are carbenes; the singlet carbenes are more stable than the triplet ones.

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Section: Resultssupporting

confidence: 53%

Theoretical study of structural patterns in CH2OP2 isomers

et al. 2010

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“…Such three-membered heterocycles were also found to be accessible by chloride abstraction from C -phosphino P -chlorophosphonium ylides . Reaction of 112 with GaCl 3 directly provided the spiro bicyclic derivative 110c in dichloromethane, but in acetonitrile, the transient diphosphinocarbocation 109c was trapped and the [3 + 2]-cycloadduct 113 was obtained regioselectively (Scheme ).…”

Section: Reactivitymentioning

confidence: 99%

Stable Noncyclic Singlet Carbenes

2009

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“…A general synthetic route to 1s 4 , 3s 2 -diphosphaallenes (R 3 PQCPR 0 ) has been reported. 105 The strategy relies upon the deprotonation of species [R 3 PQCHPR'] + with LiN(SiMe 3 ) 2 . Reaction of RCl 2 SiC(Cl)QPMes* with t BuLi results in the formation of the lithiate RCl 2 SiC(Li) = PMes* 54.…”

Section: Reaction Of the Terminal Phosphido Complex [Na(thf)mentioning

confidence: 99%

Nitrogen, phosphorus, arsenic, antimony and bismuth

Lynam

2006

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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This chapter reviews the literature reported during 2005 on the chemistry of nitrogen, phosphorus, arsenic, antimony and bismuth. PreambleOnce again the study of the chemistry of the pnictogens has provided considerable challenges to both synthetic and theoretical chemists. Significant new advances and insights into have been made, of particular note are the developments in the areas of activation of dinitrogen, such as the work of Schrock on molybdenum complexes 1,2 and the discovery of an amido-hydride complex from activation of ammonia. 3 Further highlights include the continued expansion of the use of metal phosphinidene complexes as synthetic reagents for the production of novel phosphoruscontaining materials and the synthesis of several new cationic arsenic-containing species.As in previous years and due to space restrictions this review will not, in general, consider the use of the trivalent elements as ligands, however reviews on ''user friendly'' primary phosphines 4 and how to evaluate the net donor abilities of phosphines 5 have appeared. NitrogenThe activation of dinitrogen remains a major area of interest. The molybdenumcentred reduction of dinitrogen to ammonia remains one of the most impressive methods of nitrogen fixation and a review on this subject has appeared 1 as has a comprehensive study into several aspects of this chemistry. 2 It has been shown that under an atmosphere of N 2 , the dimer [Ta(Z 5 -C 5 Me 4 R)] 2 (m-Cl) 4 (R = Me, Et) disproportionates to give [Ta(Z 5 -C 5 Me 4 R)] 2 (m-Z 1 ,Z 1 -N 2 ) as the nitrogen-containing product. 6 The dinitrogen may be considered to have undergone a four-electron reduction with the tantalum now existing in the (V) oxidation state. In a similar fashion, reduction of [Ti(Z 5 -C 5 Me 5 )Cl 3 ] in the presence of substituted fulvene gives rise to dinuclear species containing a (m-Z 1 , Z 1 -N 2 ) ligand. 7 The reduction of the zirconium complex [NPN]ZrCl 2 (thf) [NPN = PhP(CH 2 SiMe 2 NPh) 2 ] under nitrogen results in the formation of [NPN]Zr(m-Z 2 , Z 2 -N 2 )(thf). 8 A similar reaction with the titanium analogue results in the insertion of dinitrogen into the Ti-PPh bond and formation of 1. Using a related ligand set within the coordination sphere of tantalum, Fryzuk has also shown that it is possible to convert hydrazine to bridging Ta-NH-Ta groups. 9 A reaction of the same precursor with Me 2 NNH 2 results in the formation of a complex containing a bridging nitride ligand. The oxidative addition

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C‐Phosphoniophosphaalkenes as Precursors of 1σ⁴,3σ²‐Diphosphaallenes: Scope and Limitations

Cited by 14 publications

References 16 publications

Theoretical study of structural patterns in CH2OP2 isomers

Theoretical study of structural patterns in CH2OP2 isomers

Stable Noncyclic Singlet Carbenes

Nitrogen, phosphorus, arsenic, antimony and bismuth

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