A 2-ethoxycarbonylphosphaferrocene was reduced to the corresponding 2-hydroxymethyl derivative, which was condensed with pyrrole in a 2:1 ratio in the presence of BF 3 to give a phosphaferrocene−pyrrole−phosphaferrocene pincer ligand. This tridentate ligand, in turn, reacted with [Rh(acac)(CO) 2 ] to yield a rhodium carbonyl pincer complex. This complex was characterized by X-ray crystal structure analysis and tested in the hydroformylation of internal olefins.
The activation of CS 2 by the 2H-phosphindole complex with a low-coordinate phosphadiene moiety is reported. The successive hetero-Diels− Alder reaction between 2H-phosphindoles and CS 2 constructs two bridged rings and one spirocycle simultaneously, affording structurally complex P,Spolycyclic products. The two 2H-phosphindoles approach the C�S bond in a head-to-head disposition to minimize steric hindrance. This work reveals the unique reactivity of low-coordinate organophosphorus species and their potential applications in small molecule activation.
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.
Push–pull complexation: Transient terminal phosphinidene complexes [RPW(CO)5] insert at 110 °C into the BH bonds of LBH3 (L = Et3N, Ph3P; see scheme). The reaction is probably driven by an interaction between the nucleophilic boron and the electrophilic phosphorus.
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