319905-26-5Relevant academic research and scientific papers
Synthesis and properties of iron-group hydrido-cyano complexes fraiM-[MH(CN)(L)2], M = Fe, Ru or Os, L = diphosphine, and their hydrogen, trifluoroboron and triphenylboron isocyanide derivatives of the type mzws-[MH(CNH)(L)2]O3SCF3, 1mm[MH(CNBX3)(L)2], X = F or Ph, and fra/tf-[M(H2)(CNBF3)(dppp)2]BF4
Rocchini, Eliana,Rigo, Pierluigi,Mezzetti, Antonio,Stephan, Tim,Morris, Robert H.,Lough, Alan J.,Forde, Cameron E.,Fong, Tina P.,Drouin, Samantha D.
, p. 3591 - 3602 (2007/10/03)
Complexes trans-[MH(CN)L2] l {L = PPh2(CH2)PPh2, n = l (dppm), 2 (dppe) or 3 (dppp), and PR2CH2CH2PR2, R = Et (depe) or/wra-tolyl (dtpe), M = Fe (for dppe, depe and dtpe only), Ru or Os} were prepared by displacing with cyanide the halide from /raiw-[MH(X)LJ, X = Br or CI, or dihydrogen from /ra/js-[Ru(H2)H(dppe)2]BPh4. Systematic trends in the IR and 'H, P and I3C NMR and electrochemical properties are noted. The addition of one equivalent of HOTf (HO3SCF3) or [HPPh3]OTf to /ranj-[MH(CN)L2] 1 with n =1,2 or 3 usually produces the hydrogen isocyanide complexes -[MH(CNH)L2]OTf 2. The use of CN or C15N in compounds 1 provides evidence for the MCNH coordination mode over MNCH. Protonation at the M-H bond to give dihydrogen complexes trans[M(H2)(CN)L2]+ occurs to a small degree for M = Ru, /; = 1 or 3, in CH2C12 and completely for M = Os, L = depe. The use of HBF.,- Et2O results in a variety of products including /ra;;s-[MH(CNH)L2]BF4 2, fr+. The dihydrogen ligand in the last compound with M = Ru, L = dppp, is readily replaced by r|'-BF4-. Structures of the compounds 2 (M = Ru, L = dppe), /ra/w-[RuH(CNBF3)(dppe)2] and 2° (M = Os, L = dppe) are reported. The CNH ligand is a good hydrogen-bond donor so that NH ... O or NH ...F hydrogen bonds with the counter ion are formed. The reaction of BPh4- with the CNH ligand of 2 (M = Ru, L = dppe) produces /raHS-[Ru(H)(CNBPh3)(dppe)2], the structure of which is reported. Therefore the CNH ligand reacts readily with BX4- (X = F or Ph) to produce CNBX3~ ligands and HX. The Royal Society of Chemistry 2000.
