Crystal Structure of 4-Bromo benzoylmethylenediphenyldiphenylphosphinomethylphosphorane

Sabounchei, Seyyed Javad; Samiee, Sepideh; Morales‐Morales, David; Hernández‐Ortega, Simón

doi:10.2116/xraystruct.27.3

Cited by 3 publications

(2 citation statements)

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“…The multiple bond character of the ReN and CN bonds is reflected by the short Re–N (1.789(3) Å) and N–C (1.302(5) Å) distances. The Re–N distance is slightly shorter than those of reported rhenium azavinylidene complexes L n ReNCR 2 , − , but it is slightly longer than those of reported rhenium imido complexes L n ReNR. − The C–N distance is slightly longer than those of reported azavinylidene complexes. − , The C(1)–P distance (1.781(3) Å) is appreciably longer than that of the PC double bond (1.712(2) Å), but it is slightly shorter than that of the  P – C H 2 single bond (1.808 (2) Å) in Ph 2 PCH 2 PPh 2 C(H)C(O)C 6 H 4 - p -Br . The structural data indicate that both resonance structures 8a(A) and 8a(B) contribute to the structure of 8a , with the former being more important (Scheme ).…”

Section: Results and Discussionmentioning

confidence: 77%

“…[18][19][20]11 The C(1)−P distance (1.781(3) Å) is appreciably longer than that of the PC double bond (1.712(2) Å), but it is slightly shorter than that of the P−CH 2 single bond (1.808 (2) Å) in Ph 2 PCH 2 PPh 2 C(H)C(O)C 6 H 4 -p-Br. 25 The structural data indicate that both resonance structures 8a(A) and 8a(B) contribute to the structure of 8a, with the former being more important (Scheme 3). Thus, the complex can be best described as an azavinylidene complex.…”

Section: ■ Results and Discussionmentioning

confidence: 96%

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Azavinylidene Complexes from Coupling Reactions of Organonitriles with Phosphines

et al. 2021

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The reactions of the rhenium(III)-phosphine complex ReCl 3 (PMePh 2 ) 3 with organonitriles (NCR) were studied and found to give novel addition as well as simple substitution products. Refluxing ReCl 3 (PMePh 2 ) 3 in acetonitrile (MeCN) yielded a mixture of the organonitrile rhenium complex ReCl 3 (PMePh 2 ) 2 (NCMe) and the rhenium phosphonium-substituted azavinylidene complex ReCl 3 (PMePh 2 ) 2 {NC(PMePh 2 )-Me}. Similarly, reactions of ReCl 3 (PMePh 2 ) 3 with arylnitriles p-R-C 6 H 4 CN (R = H, Me, and Br) gave the corresponding azavinylidene complexes ReCl 3 (PMePh 2 ) 2 {N C(PMePh 2 )(p-C 6 H 4 R)}. The nitrile complex ReCl 3 (PPh 3 ) 2 (NCPh) is unreactive toward external PPh 3 , but it reacts with excess PMe 3 to produce the azavinylidene complex ReCl 3 (PMe 3 ) 2 {NC(PMe 3 )Ph}. Computational studies reveal the effect of ligand and substituent of organonitriles on the thermodynamics and kinetics for the reactions of ReCl 3 (PR 3 ) 2 (NCR′) with PR 3. Both the experimental and computational results indicate that nucleophilic addition of phosphines to coordinated nitriles is more favorable for nitriles with an electron-withdrawing group and for phosphines which are more electron-donating.

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