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This paper reports the study by NMR spectroscopy and ab initio methods of the structure of 3,4-dimethyl-1-cyanophosphole and its dimer. The dimer presents a PP interaction of the pnictogen type due to the presence of s-holes. NMR of the monomer was recorded in CDCl3 solution while NMR of the dimer corresponds to the solid state (CPMAS) experiments. The 2pJPP spin-spin coupling constant has not been measured, but calculated at the B3LYP level. AIM, NBO and ELF methodologies have been used to describe the electronic structure of the dimer. © 2013 Académie des sciences. Published by Elsevier Masson SAS. All rights reserved.

The nucleophilic attack of N-methylimidazole at the bridge phosphorus of a 7-phosphanorbornadiene pentacarbonylmolybdenum complex induces the collapse of the bridge. According to DFT calculations, the resulting zwitterion displays a very long and weak P - Mo bond. The excess of, N-methylimidazole thus appears to be able to displace the phosphinidene from its molybdenum complex. The final result is a phosphinidene- N-methylimidazole adduct whose structure has also been computed. When applied to the phenyl derivative at 40°C in toluene, this reaction effectively generates the [PhP] adduct, which decomposes to give essentially Ph 4P 4 and Ph 5P 5. At 80°C, PhPH 2 is also produced. In the presence of CCl 4 the phosphinidene adduct inserts into the C-Cl bond to give PhP(Cl)CCl 3. © 2006 American Chemical Society.

The transient phosphinidene complex [PhP-Mo(CO) 5], as generated from the appropriate 7-phosphanorbornadiene complex at 110°C in toluene, selectively reacts with the C=≡C triple bond of 4-phenyl-3-butyn-1-ol to give the corresponding phosphirene complex 4. Upon further heating, this phosphirene evolves via two pathways. The minor pathway involves the formal addition of the OH bond of the alcohol function onto the phosphirene P-C ring bond to give the 3-benzylidene-1,2-oxaphospholane complex 5. The major pathway involves the reaction of a second molecule of [PhP-Mo(CO) 5] with the OH group of 4, giving an intermediate phosphirene with an additional secondary alkoxyphosphine functionality (7). An intramolecular hydrophosphination of one P-C bond of the phosphirene ring then immediately takes place to give the cis-1,2-bis(phosphino)ethene [MoCCO) 4] complex 8 as a mixture of two diastereomers. After methylation of the PH group of 8, decomplexation can be efficiently achieved by reaction with sulfur. Structures have been ascertained by X-ray analysis for 5, 8, and the disulfide 10.

The nucleophilic attack of N-methylimidazole at the bridge phosphorus of a 7-phosphanorbornadiene pentacarbonylmolybdenum complex induces the collapse of the bridge. According to DFT calculations, the resulting zwitterion displays a very long and weak P - Mo bond. The excess of, N-methylimidazole thus appears to be able to displace the phosphinidene from its molybdenum complex. The final result is a phosphinidene- N-methylimidazole adduct whose structure has also been computed. When applied to the phenyl derivative at 40°C in toluene, this reaction effectively generates the [PhP] adduct, which decomposes to give essentially Ph 4P 4 and Ph 5P 5. At 80°C, PhPH 2 is also produced. In the presence of CCl 4 the phosphinidene adduct inserts into the C-Cl bond to give PhP(Cl)CCl 3. © 2006 American Chemical Society.

The transient phosphinidene complex [PhP-Mo(CO) 5], as generated from the appropriate 7-phosphanorbornadiene complex at 110°C in toluene, selectively reacts with the C=≡C triple bond of 4-phenyl-3-butyn-1-ol to give the corresponding phosphirene complex 4. Upon further heating, this phosphirene evolves via two pathways. The minor pathway involves the formal addition of the OH bond of the alcohol function onto the phosphirene P-C ring bond to give the 3-benzylidene-1,2-oxaphospholane complex 5. The major pathway involves the reaction of a second molecule of [PhP-Mo(CO) 5] with the OH group of 4, giving an intermediate phosphirene with an additional secondary alkoxyphosphine functionality (7). An intramolecular hydrophosphination of one P-C bond of the phosphirene ring then immediately takes place to give the cis-1,2-bis(phosphino)ethene [MoCCO) 4] complex 8 as a mixture of two diastereomers. After methylation of the PH group of 8, decomplexation can be efficiently achieved by reaction with sulfur. Structures have been ascertained by X-ray analysis for 5, 8, and the disulfide 10.