81626-08-6Relevant articles and documents
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.
