Heating [Rh(dtbpy)(CH
2CMe
2C
C6H
4)(Rh-C
C)(CH
2CMe
2Ph)] (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)(CH
2CMe
2C
C6H
4)(Rh-C
C)(C
6H
4-tBu-2)]. Refluxing [Ir(dtbpy)(CH
2CMe
2C
C6H
4)(Ir-C
C)(C
6H
4-tBu-2)] with 2-phenylpyridine in toluene afforded [Ir(dtbpy)(CH
2CMe
2Ph)Cl(ppy)], which was deportonated by nBuLi to give the bis-cyclometalated compound [Ir(dtbpy)(CH
2CMe
2C
C6H
4)(Ir-C
C)(ppy)]. Reaction of [Ir(dtbpy)(CH
2CMe
2C
C6H
4)(Ir-C
C)(C
6H
4-tBu-2)] with 4-(2-pyridyl)benzaldehyde or benzaldehyde led to decarbonylation of the formyl group and afforded [Ir(dtbpy)(CH
2C
CMe
2Ph)(Ir-C)(CO)(R)] (R = 4-(2’-pyridyl)phenyl, phenyl). Treatment of [M(dtbpy)(CH
2CMe
2Ph)(OTs)
2(H
2O)] (M = Rh, Ir) with Na[BAr
F...[
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Heating [Rh(dtbpy)(CH
2CMe
2C
C6H
4)(Rh-C
C)(CH
2CMe
2Ph)] (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)(CH
2CMe
2C
C6H
4)(Rh-C
C)(C
6H
4-tBu-2)]. Refluxing [Ir(dtbpy)(CH
2CMe
2C
C6H
4)(Ir-C
C)(C
6H
4-tBu-2)] with 2-phenylpyridine in toluene afforded [Ir(dtbpy)(CH
2CMe
2Ph)Cl(ppy)], which was deportonated by nBuLi to give the bis-cyclometalated compound [Ir(dtbpy)(CH
2CMe
2C
C6H
4)(Ir-C
C)(ppy)]. Reaction of [Ir(dtbpy)(CH
2CMe
2C
C6H
4)(Ir-C
C)(C
6H
4-tBu-2)] with 4-(2-pyridyl)benzaldehyde or benzaldehyde led to decarbonylation of the formyl group and afforded [Ir(dtbpy)(CH
2C
CMe
2Ph)(Ir-C)(CO)(R)] (R = 4-(2’-pyridyl)phenyl, phenyl). Treatment of [M(dtbpy)(CH
2CMe
2Ph)(OTs)
2(H
2O)] (M = Rh, Ir) with Na[BAr
F4] afforded [{M(dtbpy)(CH
2CMe
2Ph)(OTs)(H
2O)}
2(μ-OTs)
2]
2[BAr
F4]
2 (M = Rh, Ir), which can catalyze H/D exchange of THF with D
2O.
Transmetalation of [Ru(dtbpy)(NO)Cl
3] with Me
3CCH
2Li and Me
3SiCH
2MgCl afforded the trialkyl compounds [Ru(dtbpy)(NO)(R)
3] (R = CH
2CMe
3, CH
2SiMe
3). Protonation of [Ru(dtbpy)(NO)(R)
3] with HCl afforded [Ru(dtbpy)(NO)(R)
2Cl] (R = CH
2CMe
3, CH
2SiMe
3). Chloride abstraction of [Ru(dtbpy)(NO)(CH
2CMe
3)
2Cl] with silver triflate (AgOTf) afforded [Ru(dtbpy)(NO)(CH
2SiMe
3)
2(OTf)], which reacted with NH
2R to yield amine adducts [Ru(dtbpy)(NO)(CH
2SiMe
3)
2(NH
2R)][OTf] (R = tBu, mes, p-tol). [Ru(dtbpy)(NO)(CH
2SiMe
3)
2(OTf)] reacted with sodium phenoxide, siloxides and thiolates to afford [Ru(dtbpy)(NO)(CH
2SiMe
3)
2(OR)] (R = Ph, SiMe
3, SiPh
3, Si(OtBu)
3) and [Ru(dtbpy)(NO)(CH
2SiMe
3)
2(SR)] (R = xyl, SiPh
3) (xyl = 2,6-dimethylphenyl), respectively. Treatment of [Ru(dtbpy)(NO)(CH
2SiMe
3)
2(OTf)] with KOAc and K[NOsO
3] gave [Ru(dtbpy)(NO)(CH
2SiMe
3)
2(OAc)] and dimetallic [Ru(dtbpy)(NO)(CH
2SiMe
3)
2(NOsO
3)] respectively. Treatment of [Ru(dtbpy)(NO)(CH
2SiMe
3)
3] with SBA-15 resulted in elimination of one equivalent of SiMe
4. Spectroscopic data suggested that the Ru-grafted species was the alkyl species [Ru(dtbpy)(NO)(CH
2SiMe
3)
2(SBA-15)].
Treatment of [Ru(L)(NO)Cl
3] (L = bpy, 2 tBupy) with NaSC
6F
4H afforded the photolabile nitrosyl thiolate compounds [Ru(L
2)(NO)(SC
6F
4H)
3] (L
2 = bpy, 2tBupy). Reaction of Ru(NO)Cl
3⋅H
2O with NaSC
6F
4H and Na(S-tBu) yielded the dimer [{Ru(NO)(SC
6HF
4)
2}
2(μ-O)(μ-SC
6HF
4)
2Na] and trimer [{Ru(NO)(S-tBu)}
3(μ
2-S-tBu)
3(μ
3-O)(μ
3-S)Na] respectively.
Treatment of M(P) (M = H
2, Mn, Co, Ni; P
2- = tetrakis[4’-(2”-pyridyl)phenyl]porphyrin dianion) with [Cp*IrCl
2]
2 (Cp* = η
5-C
5Me
5) and NaOAc afforded the cyclometalated compounds [M{P(Cp*IrCl)
4}] (M = H
2, Mn, Co, Ni). Treatment of M(P) (M = Co, Ni) with [(η
6-arene)RuCl
2]
2 (arene = p-cymene, C
6H
6) and NaOAc afforded the bimetallic porphyrins [M{P((η
6-arene)RuCl)
4}] (M = Co, Ni; arene = C
6H
6, p-cymene).
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