28240-68-8Relevant academic research and scientific papers
1,3,2-Dithiaphospholanes with an annelated 1,2-dicarba-closo- dodecaborane(12) unit: Formation and reactivity
Wrackmeyer, Bernd,Klimkina, Elena V.,Milius, Wolfgang
, p. 5021 - 5043 (2014/04/03)
1,3,2-Dithiaphospholanes were prepared, containing an annelated 1,2-dicarba-closo-dodecaborane(12) unit, bearing halogens (F, Cl, Br, and I), H, NEt2, OEt groups, or organo substituents (R = i-Pr, t-Bu, Cy, 3,5-Me2-C6H3-CH2, Ph) at phosphorus. The t-Bu derivative was structurally characterised as its sulfide. The organo-substituted derivatives escape the ring strain by irreversible (R = t-Bu; X-ray analysis) or reversible dimerisation, by which 10-membered rings are formed. Using 1,1-bis(dichlorophosphino)methane, another dimer containing a 14-membered ring could be isolated and structurally characterised. The preferred conformation of the 1,3,2-dithiaphospholanes depends on the nature of the substituent at phosphorus. For instance, the substituents R = t-Bu, NEt 2 prefer the equatorial position, as indicated by diagnostic NMR data, supported by DFT calculations [B3LYP/6-311+G(d,p) level of theory]. The calculations also predict the tendency for dimerisation, and calculated NMR parameters are in good agreement, in most cases, with experimental data.
Design and synthesis of phosphonate inhibitors of glutamine synthetase
Farrington,Kumar,Wedler
, p. 2062 - 2067 (2007/10/02)
Inhibitors 1-4 have been shown previously to undergo enzymatic phosphorylation by glutamine synthetase (GS). Phosphonates 6-9 were designed as chemically stable analogues of these phosphorylated inhibitors, incorporating either a tetrahedral sulfur group
Synthesis and Properties of Open-Chain and Cyclic 1λ3,3λ3-Diphosphaalkanes RR'P-CH2-PR'R
Schmidbaur, Hubert,Schnatterer, Stefan
, p. 2832 - 2842 (2007/10/02)
Disecondary methylenediphosphanes R(X)PCH2P(X)R with their adjustable positive or negative polarity (X = H, Cl), which are useful building blocks for organophosphorus synthesis, were prepared by multi-step substitution of chlorine atoms in methylenebis(di
LINEARE OLIGOPHOSPHAALKANE XIII.TRIPHOSPHAALKANE MIT DEM P-C-P-C-P-DONORSKELETT; LIGANDEN FUER DEN AUFBAU VON MEHRKERNKOMPLEXEN
Brauer, David J.,Hietkamp, Sibbele,Sommer, Herbert,Stelzer, Othmar,Mueller, Gerhard,et al.
, p. 411 - 434 (2007/10/02)
The triphosphaalkane Cl2PCH2PClCH2PCl2 (III) is formed as a by-product in the synthesis of Cl2PCH2PCl2 (II).On treating III with MeMgCl or EtOH (in the presence of a base), the methyl or ethoxy derivative (V or VI) may be obtained in satisfactory yields.With Ni(CO)4 or Fe2(CO)9 V forms trinuclear complexes nM>PMe2CH2PMen>CH2PMe2n> (X, XIII; M = Fe, Ni; n = 4, 3) or binuclear stable six-membered chelate ring systems n>PMe(CH2PMe2)2m> (IX, XIV; M = Fe, Ni; n = 4, 3; m = 3, 2).An excess of Fe2(CO)9 (molar ratio V/Fe2(CO)9 1/5) yields XI with an Fe-Fe bond or the cluster XII, respectively.In both cases V bridges the Fe-Fe bond with a P-C-P donor set.X-ray structural analysis of X (triclinic, space group P1) exhibits a staggered arrangement of the three metal carbonyl fragments bound to the "stretched" P-C-P-C-P skeleton of V (Fe(1)-P(1) 2.236(1), Fe(2)-P(2) 2.226(1), Fe(3)-P(3) 2.231(1) Angstroem, P(1)-C(13)-P(2) 126.7(1), P(2)-C(14)-P(3) 127.6(1) deg).In XI (monoclinic, space group P21/n) one P-C-P donor set together with the two iron atoms Fe(2) and Fe(3) form a stable five-membered Fe2P2C ring (Fe(2)-Fe(3) 2.705(1), Fe(2)-P(2) 2.251(1), Fe(3)-P(3) 2.239(1) Angstroem).The third phosphorus atom P(1) binds an Fe(CO)4 group (Fe(1)-P(1) 2.245(1) Angstroem).The structure of cluster compound XII (monoclinic, space group P21/n) is derived from that of Os3(CO)12.One P-C-P donor set of V replaces two CO groups in equatorial positions, forming a stable Fe2P2C five-membered ring.The remaining donor position of V coordinates with an Fe(CO)4 group.
Oligophosphaalkanes, VI. Syntheses and NMR Spectroscopic Characterization of PH-functional Methylene Bridged Diphosphanes R2P-CH2-PRH and HRP-CH2-PRH
Hietkamp, Sibbele,Sommer, Herbert,Stelzer, Othmar
, p. 3400 - 3413 (2007/10/02)
1,3-Diphosphapropane, H2P-CH2-PH2 (1) was synthesized in about 40 percent yield by reduction of Cl2P-CH2-PCl2 with LiAlH4.The mono-, di-, and tri-substituted derivatives RHP-CH2-PH2 (R = iPr, CH2Ph, 3a, b) RHP-CH2-PHR (R = iPr, CH2Ph, tBu, 5a - c), R2P-CH2-PRH (R = Me, iPr, CH2Ph, 10b, 7a, b) are accessible using Cl2P-CH2-PCl2 as a starting material.A multiple stage synthesis based on MePCl2 affords the disecondary phosphane MeHP-CH2-PMeH (10d), which in contrast to reports given in the literature is thermally stable to at least 100 deg C.The 31P and 1H NMR spectra of 1 have been analyzed and simulated by use of computer programs.The structure of the phosphanes is discussed on the basis of their 1H, 31P, 31P, and 13C NMR spectra.
