16009-56-6Relevant academic research and scientific papers
Preparation and characterization of diarylphosphazene and diarylphosphinohydrazide complexes of titanium, tungsten and ruthenium and phosphorylketimido complexes of rhenium
Cowley, Andrew R.,Dilworth, Jonathan R.,Nairn, Alison K.,Robbie, Alasdair J.
, p. 680 - 693 (2007/10/03)
Reaction of the proligand Ph2PN(SiMe3)2 (L1) with WCl6 gives the oligomeric phosphazene complex [WCl4(NPPh2)]n, 1 and subsequent reaction with PMe2Ph or NBu4Cl gives [WCl4(NPPh 2)(PMe2Ph)] (2) or [WCl5(NPPh 2)][NBu4] (3), respectively. DF calculations on [WCl 5(NPPh2)][NBu4] show a W=N double bond (1.756 A) and a P-N bond distance of 1.701 A, which combined with the geometry about the P atom suggests, there is no P-N multiple bonding. Reaction of L1 with [ReOX3(PPh3)2] in MeCN (X = Cl or Br) gives [ReX2(NC(CH3)P(O)Ph2)(MeCN) (PPh3)] (X = Cl, 4, X = Br, 5) which contains the new phosphorylketimido ligand. It is bound to the rhenium centre with a virtually linear Re-N-C arrangement (Re-N-C angle = 176.6°. when X = Cl) and there is multiple bonding between Re and N (Re-N = 1.809(7) A when X = Cl). The proligand Ph2PNHNMe2 (L2H) reacts with [(C 5H5)TiCl3] to give [(C5H 5)TiCl2(Me2NNPPh2)] (6). An X-ray crystal structure of the complex shows the ligand (L2) is bound by both nitrogen atoms. Reaction of the proligands Ph2PNHNR2 [R2 = Me2 (L2H), -(CH2CH 2)2NCH3 (L3H), (CH 2CH2)2CH2 (L4H)] with [{RuCl(μ-Cl)(η6-p-MeC6H4Pr)} 2] gave [RuCl2(η6-p-MeC6H 4Pr)(L)] {L = L2H (7), L3H (8), L4H (9)}. The X-ray crystal structures of 7-9 confirmed that the phosphinohydrazine ligand is neutral and bound via the phosphorus only. Reaction of complexes 7-9 with AgBF4 resulted in chloride ion abstraction and the formation of the cationic species [RuCl(η6-p-MeC6H 4Pr)(L)]+BF4{(L = L2H (10), L 3H (11), L4H (12)}. Finally, reaction of complex 6 with [{RuCl(μ-Cl)(η6-p-MeC6H4Pr)} 2] gave the binuclear species [(η6-p-MeC 6H4Pr)Cl2Ru(μ2,η3- PNNMe2)TiCl2C5H5)], 13. The Royal Society of Chemistry 2005.
(1)H NMR study of monomeric chloro-rhenium(III) complexes with triarylphosphines and nitriles
Pearson, Celine,Beauchamp, Andre L.
, p. 13 - 18 (2008/10/08)
ReCl3(RCN)(PR')2 complexes (R = Me, Et, Ph; R' = Ph, p-tol, m-tol) give relatively narrow (1)H NMR signals in spite of the presence of the paramagnetic Re(III) centre. The signals of one ligands are not greatly affected by changes in the other ligand. In all cases, the spectra are consistent with the mer-trans structure previously found in the solid state for ReCl3 (MeCN)(PPh3)2. For P (m-tol)3, the preparation of the ReOCl3{P(m-tol)3}2 starting complex from ReO4(1-) requiered molder condition than for PPh3 and P(p-tol)3, the standard method leading to the further reduced compound ReCl4{P(m-tol)3}2, whose crystal structure was determinated by x-ray diffraction (monoclinic, P2(1)/c, a = 11.218, b = 18.204, c = 11.192?, β = 118,63°, R = 0.042). The latter complex adopts the trans geometry with the Re atom sitting on a crystalographic inversion centre.
