Treatment of [ⁿBu₄N][Ru(N)CI₄] with Na(OC₆F₅), Na(OC₆Br₅) and Na(OC₆F₄H) afforded [ⁿBu₄N][Ru(N)(OC₆F₅)₄], [ⁿBu₄N][Ru(N)(OC₆Br₅)₄] and [ⁿBu₄N][Ru(N)(OC₆F₄H)₄], respectively. Treatment of [ⁿBu₄N][Os(N)CI₄] with Na(OC₆F₅), Na(OC₆Br₅) and Na(OC₆F₄H) afforded [ⁿBu₄N][Os(N)(OC₆F₅)₄], [ⁿBu₄N][Os(N)(OC₆Br₅)₃CI] and [ⁿBu₄N][Os(N)(OC₆F₄H)₃CI], respectively. ⁿ _{4 4 6 4} ⁿ _{4 6 4 4} ⁿ _{4 4} ⁿ _{4 4 2 2} ⁿ _{4 2} ⁿ _{4 2 3} ⁿ _{4 4 6 4} ⁿ _{4 6 5 4} ⁿ _{4 6 5 4 3}...[ Read more ]

Treatment of [ⁿBu₄N][Ru(N)CI₄] with Na(OC₆F₅), Na(OC₆Br₅) and Na(OC₆F₄H) afforded [ⁿBu₄N][Ru(N)(OC₆F₅)₄], [ⁿBu₄N][Ru(N)(OC₆Br₅)₄] and [ⁿBu₄N][Ru(N)(OC₆F₄H)₄], respectively. Treatment of [ⁿBu₄N][Os(N)CI₄] with Na(OC₆F₅), Na(OC₆Br₅) and Na(OC₆F₄H) afforded [ⁿBu₄N][Os(N)(OC₆F₅)₄], [ⁿBu₄N][Os(N)(OC₆Br₅)₃CI] and [ⁿBu₄N][Os(N)(OC₆F₄H)₃CI], respectively.

Treatment of [ⁿBu₄N][Ru(N)CI₄] with Li(SC₆F₄H) and Li(SxyI) (xyI = 2,6-dimethylphenyl) afforded [ⁿBu₄N][Ru(N)(SC₆F₄H)₄] and [ⁿBu₄N][Ru(N)(Sxyl)₄], respectively. Reaction of [ⁿBu₄N][Ru(N)CI₄] with Li₂(tdt) (H₂tdt = 3,4-toluenedithiol) gave [ⁿBu₄N][Ru(N)(tdt)₂] along with a minor product [ⁿBu₄N]₂[Ru(tdt)₃]. Treatment of [ⁿBu₄N][Os(N)CI₄] with Li(SC₆F₄H) afforded [ⁿBu₄N][Os(N)(SC₆F₅)₄]. Treatment of [ⁿBu₄N][Ru(N)(OC₆F₅)₄] with excess PMe₃ afforded cis-[Ru^II(PMe₃)₄(H₂O)CI][OC₆F₄H]. Treatment of [ⁿBu₄N][Ru(N)(SC₆F₄H)₄] with 1 equiv. of MeOTf (OTf = triflate) afforded [ⁿBu₄N][Ru(N)(SC₆F₄H)₃(OTf)]. Treatment of [ⁿBu₄N][Ru(N)CI₄] with 2 equiv. of K[N(Ph₂PS)₂] and 2 equiv. of Bupy (Bupy= 4-tert-butylpyridine) afforded trans-[ⁿBu₄N][Ru(Bupy)₂CI₄].

Kinetics of reducton of osmium nitrido complexes with phosphines has been studied by UV-visible spectroscopy. For the reduction of [Os(N)(OC₆F₅)₃CI]^- by PPh₃, a saturation kinetics, in which rate is rather insensitive to [PPh₃] at high phosphine concentration, was observed. Such a observation is consistent with a mechanism involving binding of PPh₃ with the Os nitrido complex followed by rate limiting nitrido transfer to PPh₃. The pre-equilibrium constant (K) and rate of nitrido transfer (k) for the reduction of [Os(N)(OC₆F₄H)₃]^- in CH₂CI₂ at 23.4°C, The k and K were determined to be (15.2±0.70)x10^-3 s^-1 and 1.16±0.05 mol^-1 dm³, respectively. For the reduction of [Os(N)(OC₆F₄H)₃CI]^- by PPh₃, k and K are (4.05±0.22)x10^-3 s^-1 and 29.5±1.56 mol^-1 dm³, respectively. For reduction of [Os(N)(ER)₄]^- by PR₃ the rate was found to decrease in the orders: E: S > O; R: C₆F₅ > C₆Br₅. The ΔH^‡ and AS^‡ were determined to be 3.92±0.22 kJ mol^-1 and -1.13±0.06 kJ mol^-1 K^-1, respectively.

[M(L)(ol)₂] [M = Ir, Rh; L = L¹(1-(-((3,5-dibromosalicylidene)amino)-2,6-diisopropylbenzene)) or L²(1-(-((3,5-diiodosalicylidene)amino)-2,6-diisopropyIbenzene)); (oI)₂ = COD or (COE)₂] have been synthesized. Treatment of [ⁿBu₄N][Ru(N)CI₄] with 2 equiv. of NaL¹ afforded cis-[RuCI(N)(L¹)₂]. Treatment of [WOCI₄], [Mo(O)₂Br₂], and [Re(O)(PPh₃)₂CI₃] with 1 equiv. of Na₂L³ (L³ = (1R, 2S)-[N,N'-(3,5-di-t-butyl-2-hydroxy-benzylideneamine)-indanol] afforded cis-[WCI₂(O)(L³)], [Mo₂(O)₂(L³)₂](μ-O), and cis-[Re(O)CI(PPh₃)L³], respectively. Treatment of [Mo₂(O)₂(L³)₂](μ-O), with 1 equiv. of Bupy afforded [Mo₂(O)₂(L³)(Bupy)].