Reaction of [Ir^III(dtbpy)(κ²‐CH₂CMe₂C₆H₄)(C₆H₄t‐Bu‐2)] (1) (dtbpy = 4,4’‐di‐tert‐butyl‐2,2’‐bipyridyl) with NO₂(N₂O₄) led to para‐selective nitration of the aryl ligands and the formation of bis‐nitrated iridium(III) complex [Ir^III(dtbpy)(κ²‐CH₂CMe₂C₆H₃NO₂‐4){C₆H₃(t‐Bu‐2)(NO₂‐4)}] (2). Heating 1 with neat pentafluorothiophenol resulted in the formation of [Ir^IV(dtbpy)(SC₆F₅)₄] (3). [Ru^IVR₄] (6) has been synthesized from [Ru^III(acac)₃] and RMgX (R = 2‐methyl‐4‐methoxyphenyl). 6 is capable of catalyzing the oxidation of benzyl alcohol with tert‐butyl hydroperoxide (TBHP). _OEt ^VI ₂ ^III _{3 OEt} ^IV _{2 2 2 6 2} ^III _OEt ^IV ₂ ^III...[ Read more ]

Reaction of [Ir^III(dtbpy)(κ²‐CH₂CMe₂C₆H₄)(C₆H₄t‐Bu‐2)] (1) (dtbpy = 4,4’‐di‐tert‐butyl‐2,2’‐bipyridyl) with NO₂(N₂O₄) led to para‐selective nitration of the aryl ligands and the formation of bis‐nitrated iridium(III) complex [Ir^III(dtbpy)(κ²‐CH₂CMe₂C₆H₃NO₂‐4){C₆H₃(t‐Bu‐2)(NO₂‐4)}] (2). Heating 1 with neat pentafluorothiophenol resulted in the formation of [Ir^IV(dtbpy)(SC₆F₅)₄] (3). [Ru^IVR₄] (6) has been synthesized from [Ru^III(acac)₃] and RMgX (R = 2‐methyl‐4‐methoxyphenyl). 6 is capable of catalyzing the oxidation of benzyl alcohol with tert‐butyl hydroperoxide (TBHP).

[L_OEtRu^VI(N)Cl₂] underwent migratory insertion with [Rh^III(mes)₃] to afford [L_OEtRu^IVCl₂(μ‐N(2,4‐Me₂‐6‐CH₂C₆H₂))Rh^III(μ‐N(mes))L_OEtRu^IVCl₂] (7). Activation of a methyl C‐H bond in one of the mesityl ligands in [Rh^III(mes)₃] was observed.

[L_OEtRu^VI(N)Cl₂] reacted with [Ir^III(dtbpy)(CH₂SiMe₃)(SiMe₃)(Me)] and [Ir^III(dtbpy)R₃] to give [L_OEtRu^VICl₂(μ‐N)Ir^III(dtbpy)(CH₂SiMe₃)(SiMe₃)(Me)] (8) and [L_OEtRu^VICl₂(μ‐N)Ir^III(dtbpy)R₃] (R = 2,5‐dimethylphenyl (9); 2‐methyl‐4‐methoxyphenyl (10)). Treatment of [Pt^II(ppyH)(ppy)Cl] (ppyH = 2‐phenylpyridine) and [Pt^II(ItBu)(ItBu’)][BAr^f₄] (ItBu = 1,3‐di‐tert‐butylimidazol‐2‐ylidene; monometallated ItBu ligand represented as ItBu’; Ar^f = (3,5‐trifluoromethyl)phenyl) with [L_OEtRu^VI(N)Cl₂] afforded [L_OEtRu^VICl₂(μ‐N)Pt^II(ppy)Cl] (12) and [L_OEtRu^VICl₂(μ‐N)Pt^II(ItBu)(ItBu’)][BAr^f₄] (14), respectively. Oxidation of 12 by PhICl₂ gave [L_OEtRu^VICl₂(μ‐N)Pt^IV(ppy)Cl₃] (13). [L_OEtRu^VI(N)Cl₂] reacted with trans‐[Ir^III{iPr₂P(Se)NPiPr₂}₂(H)] to yield [L_OEtRu^VICl₂(μ‐N)Ir^III{iPr₂P(Se)NPiPr₂}₂(H)] (15).

Reactions of [L_OEtRu^VI(N)Cl₂] with [Cp₂Os^II] and [(η⁵‐Ind)₂Ru^II] (Cp = η⁵‐cyclopentadienyl; Ind = indenyl) resulted in ring slippage of the cycloolefin ligands and the formation of [{L_OEtRu^VICl₂(μ‐N)}₂Os^IICp(η¹‐C₅H₅)] (16) and [{L_OEtRu^VICl₂(μ‐N)}₂Ru^II(η⁵‐Ind)(η¹‐Ind)] (17), respectively.

Alkylation of [Ru^IV(NPPh₃)(PPh₃)₂Cl₃] with Me₃SiCH₂MgCl afforded the first trigonal bipyramidal ruthenium(IV) tri‐alkyl complex [Ru^IV(PPh₃)(CH₂SiMe₃)₃Cl] (18). 18 reacted with AgOTf (OTf = triflate) to give [Ru^IV(PPh₃)(CH₂SiMe₃)₃OTf] (19). Substitution of 19 with NaN₃ and KSCN afforded [Ru^IV(PPh₃)(CH₂SiMe₃)₃N₃] (21) and [Ru^IV(PPh₃)(CH₂SiMe₃)₃(SCN)] (22), respectively. Treatment of 19 with NaOC₆F₄H gave [Ru^IV(PPh₃)(CH₂SiMe₃)(Me)₂(OC₆F₄H)] (23) via the desilylation of the alkyl groups with the phenoxide. Treatment of 19 with 1,10‐phenathroline (phen) afforded [Ru^IIPPh₃)(phen)₂(Cl)][OTf] (20) via C–C elimination.

[Ru(dtbpy)(NO)(CH₂SiMe₃)₃] (24) and [Ru(tBu₃‐terpy)(CO)(CH₂SiMe₃)₂] (25) (tBu₃‐terpy = 4,4’,4”‐tri‐tert‐butyl‐2,2’:6’,2”‐terpyridine) have been used as molecular precursors for ruthenium‐grafted silica. Treatment of 24 and 25 with the mesoporous silica SBA‐15 in benzene at room temperature afforded the grafted species, presumably [≡SiORu(dtbpy)(NO)(CH₂SiMe₃)₂] (28), and [≡SiORu(tBu₃‐terpy)(CO)(CH₂SiMe₃)] (30), respectively. 28 and 30 have been characterized by a range of spectroscopic techniques. 1 and 19 have been immobilized on silica by heating the corresponding complexes with SBA‐15 at 60 °C. Ruthenium and rhodium‐grafted SBA‐15 have been prepared by chemical vapor deposition of [Rh(mes)₃] (mes = 2,4,6‐trimethylphenyl) and [Ru(p‐xyl)₄] (p‐xyl = 2,5‐dimethylphenyl) in vacuum at 300 °C. 28 and 30 are capable of catalyzing the oxidation of benzyl alcohol with TBHP.