Reaction of Os(por)O
2 [por = TTP, 5,10,15,20-tetra([italic]p-tolyl) porphyrinate(-II); OEP, 2,3,7,8,12,13,17,18-octaethylporphyrinate(-II)] with SOCl
2 gave Os(por)Cl
2 in good yields. Treatment of Os(por)CI
2 with RLi (R = Ph, Me
3SiCH
2) gave air-stable diamagnetic dialkyl compounds Os(por)R
2, which have been characterised by X-ray crystallography. The cyclic voltammogram of Os(TTP)Ph
2 exhibits reversible Os(V)/(IV) couple at 0.32 V [italic]vs Cp
2Fe
+/0 (Cp
2Fe = ferrocene). Oxidation of Os(TTP)Ph
2 by AgBF
4 afforded [Os
v(TTP)Ph
2][BF
4].
2 3 2 2 2 6 4 2 IV...[
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Reaction of Os(por)O
2 [por = TTP, 5,10,15,20-tetra([italic]p-tolyl) porphyrinate(-II); OEP, 2,3,7,8,12,13,17,18-octaethylporphyrinate(-II)] with SOCl
2 gave Os(por)Cl
2 in good yields. Treatment of Os(por)CI
2 with RLi (R = Ph, Me
3SiCH
2) gave air-stable diamagnetic dialkyl compounds Os(por)R
2, which have been characterised by X-ray crystallography. The cyclic voltammogram of Os(TTP)Ph
2 exhibits reversible Os(V)/(IV) couple at 0.32 V [italic]vs Cp
2Fe
+/0 (Cp
2Fe = ferrocene). Oxidation of Os(TTP)Ph
2 by AgBF
4 afforded [Os
v(TTP)Ph
2][BF
4].
Reaction of Ru(TBPP)O
2 [TBPP = 5,10,15,20-tetrakis[italic]p-[italic]t- butylphenyl)porphyrinate(-II)] with Me
3SiCl gave Ru(TBPP)Cl
2. Treatment of Ru(TBPP)Cl
2 with ArNH
2 (Ar = [italic]p-XC
6H
4NH
2, X = Me, H, Cl, I) afforded the first mono-imido-Ru
IV complexes Ru(TBPP)(NAr). Ru(TBPP)(NAr) exhibit reversible Ru(V)/Ru(IV) couple at [italic]ca 0.4 V [italic]vs Cp
2Fe
+/0. Treatment of Ru(TBPP)(NAr) with Ag
I or Ce
IV afforded [Ru
v(TBPP)(NAr)][subperscript +]. The reductions of Ru(TBPP)(NAr) by PMe
2Ph and PMe
2 and PMe
3 show saturation kinetics, suggesting binding of phosphine to the Ru(IV) complex prior to rate-limiting intramolecular imido transfer. The first-order rate constant ([italic]k[
l) and phosphine binding constant ([italic]K) for the reduction of Ru(TBPP)(NC
6H
4Me-[italic]p) by PMe
2Ph at 25.0 [degrees celsious] in toulene were determined to be 6.72 ± 0.19 x 10
-4 s
-1 and 38.4 ± 6.6 x 10
3, respectively. The activation enthalpy ([delta italic H double dagger]) and entropy ([delta italic S double dagger]) for the above reaction are 125 ± 1 kJ mol
-1 and 113 ± 21 J K
-1 mol
-1, respectively.
The Co-C stretching frequencies for Co(bpb)R(OH
2), [Co(bpb)CH
3]
+ (bpb = 1,2-bis(2-pyridinecarboxamido)benzene) and Co(por)CH
3 (por = porphyrinate(-II)) have been unambiguously determined by near-IR FT-Raman spectroscopy. Oxidation of Co(bpb)CH
3(OH
2) with Ce(IV) gave [Co
IV(bpb)CH
3]
+ characterised by EPR spectroscopy. The Co-C stretching frequencies for Co
III(bpb)CH
3(OH
2) and [Co
IV(bpb)CH
3]
+ have been determined to be 515 and 491 cm
-1, respectively.
Reactions of Li([italic]t-BuL-NS) (lithium bis(4-[italic]t-butylphenyl)-2- pyridylmethanthiolate(l-)) with MCl
2 (M = Zn, Ni, Pt) afforded the respective M([italic]t-BuL-NS)
2 complexes in good yields. Treatment of CuCl
2 and PdCl
2(PhCN)
2 with Li([italic]t-BuL-NS) afforded dimeric compounds [Cu([italic]t-BuL-NS)Cl(OH
2)]
2 and [Pd([italic]t-BuL-NS)](μ-Cl)
2, respectively. The interaction of Li([italic]t-BuL-NS) with [Ru(CO)
2Cl
2n and [Rh(cod)Cl]
2 (cod =l,5-cyclooctadiene) gave respectively, [italic]cis-[Ru([italic] t-BuL-NS)
2(CO)2] and the structurally characterised Rh([italic]t-BuL-NS)(cod). Ni, Ru and Cu complexes were found to catalyse oxidation of olefins by iodosylbenzene and [italic]tert-butylhydroperoxide. The Rh complex is an active catalyst for hydrogenation of olefin under ambient conditions.
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