304000-69-9Relevant articles and documents
The synthesis and co-ordination chemistry of new functionalised pyridylphosphines derived from Ph2PCH2OH
Durran, Scan E.,Smith, Martin B.,Slawin, Alexandra M. Z.,Steed, Jonathan W.
, p. 2771 - 2778 (2007/10/03)
Condensation of Ph2PCH2OH with H2NC5H3(OH)N in methanol/toluene gave the new "hybrid" ligand Ph2PCH2N(H)C5H3(OH)N la, which upon phosphorylation with either C1P(O)R2 (R = Ph, OPh) or C1PR2 afforded Ph2PCH2N(H)C5H3(X)N [X = OP(O)Ph2 II; OP(O)(OPh)2 III; OPPh2 IVJ. Oxidation of la with aqueous H2O2 in thf gave Ph2P(O)CH2N(H)C5H3(OH)N V. The dichloroplatinum(n) complexes 1-4 were prepared from [PtCl2(cod)] (cod = cycloocta-l,5-diene) and la, II or HI (2 equiv.) or IV (1 equiv.). Reaction of [AuCl(tht)] (tht = tetrahydrothiophene) with 1 equiv. of la gave [AuCl(Ia)] 5. Bridge cleavage of [{RuCl(u-Cl)OlVcymene)}2], [{RuCl(u-Cl)(r|6-C6Me6)}2] or [{MCl(u-Cl)(n5-C5Me5)}J (M = Rh, Ir) with la-IV afforded either monometallic [MCl2(L)(PR3)] 6-11 (M = Ru, Rh or Ir; L = rf-p-cymene, C5-C5Me5; PR3 = la, II or III) or P,P'-bridged bimetallic [{MC12(L)}2 IV] 12-15 (M = Ru, Rh or Ir; L = TI Vcymene, r|6-C6Me6, tf-CjMej) complexes. The neutral ruthenium(ii) complexes [RuCl2(nVcymene){P-Ph2PCH2N(H)C5H3(X)j] (X = OH 6a; X = H 6b) undergo isomerisation in CDCl3 to give [RuCl(n6-/)-cymene){/>,Mpyridyl)-Ph2PCH2N(H)C3H 3(X)N}]Cl (X = OH 6c; X = H 6d). In contrast aged solutions (ca. 40 d) of 7-15 show no evidence (by nP{lH} NMR) for P,W(pyridyl)chelation. The X-ray structures of representative compounds have been determined, and confirm, in the case of 6c/ 6d, a novel six-membered M-P-C-N-C-N metallacycle. The Royal Society of Chemistry 2000.
