Heating [Rh(dtbpy)(CH₂CMe₂C^C₆H₄)(Rh-C^C)(CH₂CMe₂Ph)] (dtbpy = 4,4’-di-tert-butyl-2,2’-dipyridyl) at 138°C in xylene resulted in intra-molecular C-H activation of the neophyl group and the formation of [Rh(dtbpy)(CH₂CMe₂C^C₆H₄)(Rh-C^C)(C₆H₄-tBu-2)]. Refluxing [Ir(dtbpy)(CH₂CMe₂C^C₆H₄)(Ir-C^C)(C₆H₄-tBu-2)] with 2-phenylpyridine in toluene afforded [Ir(dtbpy)(CH₂CMe₂Ph)Cl(ppy)], which was deportonated by nBuLi to give the bis-cyclometalated compound [Ir(dtbpy)(CH₂CMe₂C^C₆H₄)(Ir-C^C)(ppy)]. Reaction of [Ir(dtbpy)(CH₂CMe₂C^C₆H₄)(Ir-C^C)(C₆H₄-tBu-2)] with 4-(2-pyridyl)benzaldehyde or benzaldehyde led to decarbonylation of the formyl group and afforded [Ir(dtbpy)(CH₂C^CMe₂Ph)(Ir-C)(CO)(R)] (R = 4-(2’-pyridyl)phenyl, phenyl). Treatment of [M(dtbpy)(CH₂CMe₂Ph)(OTs)₂(H₂O)] (M = Rh, Ir) with Na[BAr^F...[ Read more ]

Heating [Rh(dtbpy)(CH₂CMe₂C^C₆H₄)(Rh-C^C)(CH₂CMe₂Ph)] (dtbpy = 4,4’-di-tert-butyl-2,2’-dipyridyl) at 138°C in xylene resulted in intra-molecular C-H activation of the neophyl group and the formation of [Rh(dtbpy)(CH₂CMe₂C^C₆H₄)(Rh-C^C)(C₆H₄-tBu-2)]. Refluxing [Ir(dtbpy)(CH₂CMe₂C^C₆H₄)(Ir-C^C)(C₆H₄-tBu-2)] with 2-phenylpyridine in toluene afforded [Ir(dtbpy)(CH₂CMe₂Ph)Cl(ppy)], which was deportonated by nBuLi to give the bis-cyclometalated compound [Ir(dtbpy)(CH₂CMe₂C^C₆H₄)(Ir-C^C)(ppy)]. Reaction of [Ir(dtbpy)(CH₂CMe₂C^C₆H₄)(Ir-C^C)(C₆H₄-tBu-2)] with 4-(2-pyridyl)benzaldehyde or benzaldehyde led to decarbonylation of the formyl group and afforded [Ir(dtbpy)(CH₂C^CMe₂Ph)(Ir-C)(CO)(R)] (R = 4-(2’-pyridyl)phenyl, phenyl). Treatment of [M(dtbpy)(CH₂CMe₂Ph)(OTs)₂(H₂O)] (M = Rh, Ir) with Na[BAr^F₄] afforded [{M(dtbpy)(CH₂CMe₂Ph)(OTs)(H₂O)}₂(μ-OTs)₂]₂[BAr^F₄]₂ (M = Rh, Ir), which can catalyze H/D exchange of THF with D₂O.

Transmetalation of [Ru(dtbpy)(NO)Cl₃] with Me₃CCH₂Li and Me₃SiCH₂MgCl afforded the trialkyl compounds [Ru(dtbpy)(NO)(R)₃] (R = CH₂CMe₃, CH₂SiMe₃). Protonation of [Ru(dtbpy)(NO)(R)₃] with HCl afforded [Ru(dtbpy)(NO)(R)₂Cl] (R = CH₂CMe₃, CH₂SiMe₃). Chloride abstraction of [Ru(dtbpy)(NO)(CH₂CMe₃)₂Cl] with silver triflate (AgOTf) afforded [Ru(dtbpy)(NO)(CH₂SiMe₃)₂(OTf)], which reacted with NH₂R to yield amine adducts [Ru(dtbpy)(NO)(CH₂SiMe₃)₂(NH₂R)][OTf] (R = tBu, mes, p-tol). [Ru(dtbpy)(NO)(CH₂SiMe₃)₂(OTf)] reacted with sodium phenoxide, siloxides and thiolates to afford [Ru(dtbpy)(NO)(CH₂SiMe₃)₂(OR)] (R = Ph, SiMe₃, SiPh₃, Si(OtBu)₃) and [Ru(dtbpy)(NO)(CH₂SiMe₃)₂(SR)] (R = xyl, SiPh₃) (xyl = 2,6-dimethylphenyl), respectively. Treatment of [Ru(dtbpy)(NO)(CH₂SiMe₃)₂(OTf)] with KOAc and K[NOsO₃] gave [Ru(dtbpy)(NO)(CH₂SiMe₃)₂(OAc)] and dimetallic [Ru(dtbpy)(NO)(CH₂SiMe₃)₂(NOsO₃)] respectively. Treatment of [Ru(dtbpy)(NO)(CH₂SiMe₃)₃] with SBA-15 resulted in elimination of one equivalent of SiMe₄. Spectroscopic data suggested that the Ru-grafted species was the alkyl species [Ru(dtbpy)(NO)(CH₂SiMe₃)₂(SBA-15)].

Treatment of [Ru(L)(NO)Cl₃] (L = bpy, 2 tBupy) with NaSC₆F₄H afforded the photolabile nitrosyl thiolate compounds [Ru(L₂)(NO)(SC₆F₄H)₃] (L₂ = bpy, 2tBupy). Reaction of Ru(NO)Cl₃⋅H₂O with NaSC₆F₄H and Na(S-tBu) yielded the dimer [{Ru(NO)(SC₆HF₄)₂}₂(μ-O)(μ-SC₆HF₄)₂Na] and trimer [{Ru(NO)(S-tBu)}₃(μ₂-S-tBu)₃(μ₃-O)(μ₃-S)Na] respectively.

Treatment of M(P) (M = H₂, Mn, Co, Ni; P^2- = tetrakis[4’-(2”-pyridyl)phenyl]porphyrin dianion) with [Cp*IrCl₂]₂ (Cp* = η⁵-C₅Me₅) and NaOAc afforded the cyclometalated compounds [M{P(Cp*IrCl)₄}] (M = H₂, Mn, Co, Ni). Treatment of M(P) (M = Co, Ni) with [(η⁶-arene)RuCl₂]₂ (arene = p-cymene, C₆H₆) and NaOAc afforded the bimetallic porphyrins [M{P((η⁶-arene)RuCl)₄}] (M = Co, Ni; arene = C₆H₆, p-cymene).