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Title: Synthesis, crystal structures, and reactivity of ruthenium and osmium nitrido complexes
Authors: Lam, Ngai Man
Issue Date: 2006
Abstract: 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-[RuII(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)].
Description: Thesis (M.Phil.)--Hong Kong University of Science and Technology, 2006
xxv, 138 leaves : ill. ; 30 cm
HKUST Call Number: Thesis CHEM 2006 LamN
Appears in Collections:CHEM Master Theses

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