Treatment of [
nBu
4N][Ru(N)CI
4] with Na(OC
6F
5), Na(OC
6Br
5) and Na(OC
6F
4H) afforded [
nBu
4N][Ru(N)(OC
6F
5)
4], [
nBu
4N][Ru(N)(OC
6Br
5)
4] and [
nBu
4N][Ru(N)(OC
6F
4H)
4], respectively. Treatment of [
nBu
4N][Os(N)CI
4] with Na(OC
6F
5), Na(OC
6Br
5) and Na(OC
6F
4H) afforded [
nBu
4N][Os(N)(OC
6F
5)
4], [
nBu
4N][Os(N)(OC
6Br
5)
3CI] and [
nBu
4N][Os(N)(OC
6F
4H)
3CI], respectively.
Treatment of [
nBu
4N][Ru(N)CI
4] with Li(SC
6F
4H) and Li(SxyI) (xyI = 2,6-dimethylphenyl) afforded [
nBu
4N][Ru(N)(SC
6F
4H)
4] and [
nBu
4N][Ru(N)(Sxyl)
4], respectively. Reaction of [
nBu
4N][Ru(N)CI
4] with Li
2(tdt) (H
2tdt = 3,4-toluenedithiol) gave [
nBu
4N][Ru(N)(tdt)
2] along with a minor product [
nBu
4N]
2[Ru(tdt)
3]. Treatment of [
nBu
4N][Os(N)CI
4] with Li(SC
6F
4H) afforded [
nBu
4N][Os(N)(SC
6F
5)
4]. Treatment of [
nBu
4N][Ru(N)(OC
6F
5)
4] with excess PMe
3 afforded cis-[Ru
II(PMe
3)
4(H
2O)CI][OC
6F
4H]. Treatment of [
nBu
4N][Ru(N)(SC
6F
4H)
4] with 1 equiv. of MeOTf (OTf = triflate) afforded [
nBu
4N][Ru(N)(SC
6F
4H)
3(OTf)]. Treatment of [
nBu
4N][Ru(N)CI
4] with 2 equiv. of K[N(Ph
2PS)
2] and 2 equiv. of Bupy (Bupy= 4-tert-butylpyridine) afforded trans-[
nBu
4N][Ru(Bupy)
2CI
4].
Kinetics of reducton of osmium nitrido complexes with phosphines has been studied by UV-visible spectroscopy. For the reduction of [Os(N)(OC
6F
5)
3CI]
- by PPh
3, a saturation kinetics, in which rate is rather insensitive to [PPh
3] at high phosphine concentration, was observed. Such a observation is consistent with a mechanism involving binding of PPh
3 with the Os nitrido complex followed by rate limiting nitrido transfer to PPh
3. The pre-equilibrium constant (K) and rate of nitrido transfer (k) for the reduction of [Os(N)(OC
6F
4H)
3]
- in CH
2CI
2 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 dm
3, respectively. For the reduction of [Os(N)(OC
6F
4H)
3CI]
- by PPh
3, k and K are (4.05±0.22)x10
-3 s
-1 and 29.5±1.56 mol
-1 dm
3, respectively. For reduction of [Os(N)(ER)
4]
- by PR
3 the rate was found to decrease in the orders: E: S > O; R: C
6F
5 > C
6Br
5. 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 = L
1(1-(-((3,5-dibromosalicylidene)amino)-2,6-diisopropylbenzene)) or L
2(1-(-((3,5-diiodosalicylidene)amino)-2,6-diisopropyIbenzene)); (oI)
2 = COD or (COE)
2] have been synthesized. Treatment of [
nBu
4N][Ru(N)CI
4] with 2 equiv. of NaL
1 afforded cis-[RuCI(N)(L
1)
2]. Treatment of [WOCI
4], [Mo(O)
2Br
2], and [Re(O)(PPh
3)
2CI
3] with 1 equiv. of Na
2L
3 (L
3 = (1R, 2S)-[N,N'-(3,5-di-t-butyl-2-hydroxy-benzylideneamine)-indanol] afforded cis-[WCI
2(O)(L
3)], [Mo
2(O)
2(L
3)
2](μ-O), and cis-[Re(O)CI(PPh
3)L
3], respectively. Treatment of [Mo
2(O)
2(L
3)
2](μ-O), with 1 equiv. of Bupy afforded [Mo
2(O)
2(L
3)(Bupy)].
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