Linear and Branched Phospha[<i>n</i>]triangulanes

Slootweg, J. Chris; Kanter, Frans J. J. de; Schakel, Marius; Lutz, Martin; Spek, Anthony L.; Kozhushkov, Sergei I.; Meijere, Armin de; Lammertsma, Koop

doi:10.1002/chem.200500538

Cited by 16 publications

(12 citation statements)

References 55 publications

(87 reference statements)

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“…Reaction at room temperature with a fivefold excess of 9 and 5 % CuCl did not improve the conversion. These observations are consistent with the proposed intermediacy of a phosphinidene–CuCl species,32, 8, 9b,c which is sterically more demanding than the “free” phosphinidene complex generated without the Cu I catalyst. Thermal decomposition of 16 at 110 °C with a fivefold excess of 9 afforded a cleaner reaction,33, but still only 31 % conversion to ( Z )‐ 4 a was obtained.…”

Section: Resultssupporting

confidence: 87%

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Fused Tricyclic Phosphiranes—Analysis of Phosphorus Chemical Shieldings

Couzijn

Ehlers

Slootweg

et al. 2008

Chemistry A European J

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1,2‐Addition of transient W(CO)5‐complexed phosphinidenes exo to hexamethyl Dewar benzene affords the novel 3‐phosphatricyclo[3.2.0.02,4]hept‐6‐ene complexes. The fused tricyclic phosphiranes are obtained as both the Z and the thermally less stable E isomers, the 31P NMR chemical shifts of which differ by about 60 ppm. A computational investigation shows that the phosphorus pyramidalization and the presence of the γ double bond are responsible for this effect. The semiquantitative results contribute to a more systematic understanding of the structural influences on 31P chemical shieldings. The congested double bond of the Z isomer can be epoxidized with m‐chloroperbenzoic acid (MCPBA) to afford a fused tetracyclic P,O bis‐adduct.

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Section: Resultssupporting

confidence: 87%

“…Steric congestion of the substrate : Substrates with two double bonds can give both single and double phosphinidene addition,9c, 29 but only the mono‐adducts were obtained in the case of hexamethyl Dewar benzene (HMDB) ( 9 ). We ascribe this to the steric congestion of the double bonds.…”

Section: Resultsmentioning

confidence: 99%

Fused Tricyclic Phosphiranes—Analysis of Phosphorus Chemical Shieldings

Couzijn

Ehlers

Slootweg

et al. 2008

Chemistry A European J

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“…318f An interesting influence of the number of spiroannelated three-membered rings on the reactivity was also observed for the branched higher phospha Moreover, along with phospha[5]-(712) and phospha [7]triangulanes (706), which were obtained in 71% and 42% yield, respectively, complex mixtures of byproducts were formed, from which the rearranged products 713 and 714 were isolated in 2% and 6% yield, respectively. It is believed 327,476 that, in contrast to the thermally induced cheletropic addition of phosphinidene R-PdW(CO) 5 It is noteworthy that an increasing number of spiroannelated cyclopropane rings leads to an increasing thermal stability of the uncomplexed branched phospha[n]triangulanes. Thus, the stabilizing W(CO) 5 group could be removed from 706 by direct ligand exchange in refluxing xylene (150°C !)…”

Section: Branched Triangulanes and Heteroanaloguesmentioning

confidence: 98%

Three-Membered-Ring-Based Molecular Architectures

2006

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“…51 Although the compound is quite thermally stable, Scheme 2 heating to 130 1C (Scheme 4) results in the formation of the two species 21 and 22 (in the case where R = Me): the isomerisation to 21 is thought to proceed via a 1phosphabutadiene. Phosphinidene ligands have also been shown to be converted into Z 1 -phosphaalkene and Z 1 -coordinated diazaphosphaallene ligands, 52 to act as precursors for 2-aminophosphindole, 53 phospha[n]triangulanes 54 and substituted phosphiranes, 55,56 An example of an in situ generation of the fluoro-substituted phosphinidene complex [FP-Mo(CO) 5 ] has been reported which may be trapped by Ph 2 C 2 and 2-dimethylbutadiene. 57 The reaction of a phosphinidene, which is stable at room temperature, with MeOTF results in a remarkable dimerisation reaction to give the bowl-shaped molecule 23 (Scheme 5).…”

Section: Phosphorusmentioning

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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Linear and Branched Phospha[n]triangulanes

Cited by 16 publications

References 55 publications

Fused Tricyclic Phosphiranes—Analysis of Phosphorus Chemical Shieldings

Fused Tricyclic Phosphiranes—Analysis of Phosphorus Chemical Shieldings

Three-Membered-Ring-Based Molecular Architectures

Nitrogen, phosphorus, arsenic, antimony and bismuth

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