87863-04-5Relevant academic research and scientific papers
Stretched H2 complexes: Structural control in ReH7{P(C6H4-p-X)3}2 (X = CH3, H, F, CF3, OMe) complexes by electronic ligand effects
Michos, Demetrius,Luo, Xiao-Liang,Howard, Judith A. K.,Crabtree, Robert H.
, p. 3914 - 3916 (2008/10/08)
A series of new or known ReH7{P(C6H4-p-X)3}2 (X = CH3 (1), H (2), F (3), CF3 (4), OMe (5)) compexes which contain isosteric phosphine ligands are studied by 1H NMR spin-lattice (T1) hydride relaxation time measurements. The T1(min) values are found to decrease as the electron-withdrawing ability of the aromatic para substituents X of the phosphines increases. A plot of log {T1x(min)/T1H(min)} against the Hammett σp constants for the substituents gives a ρ value of -0.30. The results are consistent with the formulation of 1-5 in solution as containing an elongated η2-H2 ligand with different H?H distances (for compound 1, r(H?H) = 1.357 A? by neutron diffraction) which depend primarily on the electronic character of the phosphine ligands and increase from 1.24 A? for the most electron-withdrawing phosphine P(C6H4-p-CF3)3 to 1.42 A? for the most electron-donating phosphine P(C6H4-p-OMe)3.
New Complexes of Rhenium-(V) or -(III) with Various Diphosphines or Bis(diphenylphosphino)methane Monoxide: Crystal Structure of mer-
Fontaine, Xavier L. R.,Fowles, Edmund H.,Layzell, Timothy P.,Shaw, Bernard L.,Thornton-Pett, Mark
, p. 1519 - 1524 (2007/10/02)
Treatment of or with the diphosphines, Ph2PCH2PPh2 (dppm), Ph2PC(=CH2)PPh2 (vdpp), cis-Ph2PCH=CHPPh2 (dppen), or Ph2PCHMePPh2 (1,1'-dppe) gave complexes of the type (L-L = chelating diphosphine, X=Cl or Br), in high yield.Treatment of with an excess of dppm at 20 deg C caused some reduction to give a mixture of two rhenium(III) complexes 2a and 3a, which was difficult to separate.Treatment of with 2 mol of dppm in hot benzene gave pure 2a, whilst treatment of with 4-5 mol equivalents of dppm in hot benzene gave 3a in excellent yield.The tribromide analogue was prepared by heating with dppm.On treating with dppm, was formed but this was contaminated with the isomeric salt Br from which it could not be separated; however the NMR parameters for both components were assigned.The pure salt BPh4 was prepared from the mixture.In their 1H NMR spectra, these rhenium(III) complexes show large paramagnetic shifts for the methylene protons of the chelated dppm and for some of the ortho-large paramagnetic shifts for the methylene protons of the chelated dppm and for some of the ortho-protons.Some of these resonances were assigned using two-dimensional correlation spectroscopy and nuclear Overhauser effect experiments.Crystals of complex 2a are monoclinic, space group P21/n, with a=1147.7(4), b=2315.5(6), c=2069.7(6) pm, β=91.7(3) deg and Z=4; final R factor 0.0465 for 6150 observed reflections.The structure shows octahedral co-ordination with a mer arrangement of chlorines, a chelated dppm and a monodentate dppm monoxide, with the P=O group unco-ordinated.
