The chemistry of parent phosphiranide in the coordination sphere of tungsten

Abstract

2-Chloroethylphosphine W(CO)5 complex readily reacts with sodium hydride. With one equivalent of NaH, the parent phosphirane complex is obtained. With more than two equivalents, the phosphiranide complex is exclusively formed. With 1.5 equivalents, a 1 : 1 mixture of and is obtained but readily attacks at the phosphorus atom by splitting of ethylene and by the formation of the P-P complex . In turn, the P-P bond of is split by NaH to yield the phosphide complex . The phosphiranide complex is a good source for a large variety of functional phosphirane complexes . With BrCN, the 1-cyanophosphirane complex is formed. Upon heating it loses its complexing group. Upon hydrolysis, it gives the 1-hydroxyphosphirane complex which dimerizes in basic medium by opening one P-C bond of the ring to give . The reaction of with PhPCl2 yields the triphosphorus complex whose molecular structure has been established by X-ray crystal structure analysis.

Transition‐Metal‐Like Reversible Cycloadditions of [tBuSP‐W(CO)5] with Alkenes and Alkynes

“…As shown in Scheme c, the reaction with methanol provided 10 through the insertion of [ t BuSP‐W(CO) 5 ] into the O−H bond. In contrast to 1‐( tert ‐butylthio)phosphirane complex 5, 1‐hydroxylphosphirane complex reacted with MeOH through the cleavage of one C−P bond, which was probably due to the oxygen‐induced additional polarization of C−P bond …”

“…For examples, the terminal amino‐ and ferrocenyl‐substituted phosphinidene complexes were obtained with the corresponding phosphirane complexes. Recently, we reported the generation of [EtO 2 CP‐W(CO) 5 ] and [PhC(O)P‐W(CO) 5 ] by dissociation of related phosphirane complexes at 140 °C. Our recent work on phosphiranes offers a good chance to disclose the chemistry of the unknown thio‐substituted phosphinidene complex [RSP‐W(CO) 5 ].…”

“…Phosphiranide complex 1 , which was prepared from β‐chloroethylphosphine, has been proved to be a very convenient and efficient source for a variety of 1‐substituted phosphiranes . The complexation of the phosphorus lone pair by Group VI metal carbonyls, especially W(CO) 5 , is crucial in this synthetic route, since it stabilizes the phosphiranide 1 and phosphiranes . Besides, effective W→P back‐bonding will stabilize the target thiophosphinidene.…”

The Chemistry of 1‐Acylphosphirane Complexes: A Phosphorus Analogue of the Cloke–Wilson Rearrangement

“…We worked in the coordination sphere of tungsten to gain stability and ease of purification. A preliminary experiment on a C‐unsubstituted 1‐acylphosphirane complex led to the simple decomplexation of the ring . Since we knew that phenyl substitution on the ring carbons favors the splitting of the phosphirane heterocycle, we decided to investigate the thermolysis of 1‐acyl‐2‐phenylphosphirane complexes.…”

“…Ap reliminary experiment on aC -unsubstituted 1-acylphosphirane complex led to the simple decomplexation of the ring. [4] Sincew ek new that phenyls ubstitution on the ring carbons favors the splitting of the phosphirane heterocycle, [5] we decided to investigate the thermolysis of 1-acyl-2-phenylphosphirane complexes. This led us to the discovery of the phosphorus analogue of the Cloke-Wilson rearrangement.…”