154155-86-9Relevant academic research and scientific papers
Bulky chloromethylchlorophosphines - Syntheses and reductive dehalogenation with Fe2(CO)9
Fischer, J?rg,Machnitzki, Peter,Stelzer, Othmar
, p. 883 - 894 (2007/10/03)
Chloromethylchlorophosphines R(Cl)P-CH2-Cl (R = C6H11, sec-C4H9, 2,4,6-R'3C6H2; R' = tBu, iPr) with bulky substituents (1a - 1d) have been prepared by treatment of Cl2P-CH2-Cl with organolithium compounds RLi (R = 2,4,6-R'3C6H2) or Grignard reagents RMgX (R = C6H11, sec-C4H9). For the less bulky phenyl derivative Ph(Cl)P-CH2-Cl (1i) a protected group two stage synthesis has been developed employing Et2N(Cl)P-CH2-Cl as an intermediate. Si-N cleavage reactions between Cl2P-CH2-Cl and R2N-SiMe3 or nucleophilic substitution with Ph2NH yield the amino derivatives R'2N(Cl)P-CH2-Cl (R' = Ph, Et, iPr) (1e, 1g, 1h). The chloromethylbromophosphines R(Br)P-CH2-Cl (R = Br, C6H11) have been obtained by halogen exchange in 1 and 1a with MgBr2 etherate. 1a, 1e, 1g and 1h exist preferably in an antiperiplanar conformation with respect to the P-C(H2) bond as inferred from the analysis of the 1H(CH2)-NMR spectra. Temperature dependent 1H and 13C{1H} NMR spectra indicate restricted rotational processes in 1h. On reaction of 2a with Fe2(CO)9 the η2,μ3-phosphaalkene cluster 3 is obtained, while with 2b (R = 2,4,6-iPr3C6H2) the μ3-phosphinidene cluster 4 is formed. Reductive dehalogenation of 1c (R = 2,4,6-tBu3C6H2) affords the phosphaalkene complex 6 in addition to the 2,3-dihydrobenzo[b]phosphole complex 5. Treatment of the iron carbonyl complex 7c with Fe2(CO)9 in a 1:1 molar ratio at elevated temperatures leads to a novel μ2-phosphido complex 7b with an ortho-metallated Ph2N substituent.
Chlormethylchlorphosphane R(Cl)P-CH2-Cl-Synthone fuer den Aufbau von Phosphaalkenen im Metalltemplat
Brauer, David J.,Ciccu, Antonella,Fischer, Joerg,Hessler, Gisbert,Stelzer, Othmar,Sheldrick, William S.
, p. 111 - 124 (2007/10/02)
On reaction of the chloromethylchlorophosphines R(Cl)P-CH2-Cl (R=Cl, i-Pr, t-Bu, NEt2, N(i-Pr)2, NPh2, O-2,6-i-Pr2C6H3; 1-7) with diiron enneacarbonyl the iron carbonyl complexes 8-14 are formed in good yields.Dehalogenation of the phosphine complexes 9-1
