The treatment of [Ru(CO)2Cl2]x with 4,4′,4″‐tri‐tert‐butyl‐2,2′:6′,6″‐terpyridyl (tbtpy) in tetrahydrofuran at reflux afforded trans‐[Ru(tbtpy)Cl2(CO)] (1). The alkylation of complex 1 with excess Me3SiCH2MgCl afforded a mixture of trans‐[Ru(tbtpy)(CH2SiMe3)2(CO)] (2) and trans‐[Ru(tbtpy)(CH2SiMe3)Cl(CO)] (3), whereas complex 3 could be obtained in good yield by the alkylation of complex 1 with 1 equiv. of Me3SiCH2MgCl. On the other hand, the alkylation of 1 with MeLi and PhCH2MgBr afforded the monoalkyl complexes [Ru(tbtpy)(Me)Cl(CO)] (4) and [Ru(tbtpy)(CH2Ph)Cl0.5Br0.5(CO)] (5), respectively. The crystal structure of complex 5 was determined. Complex 2 and the previously prepared mer‐[Ru(dtbpy)(CH2SiMe3)3(NO)] (dtbpy = 4,4′‐di‐tert‐butyl‐2,2′‐bipyridyl) were immobilized on SBA‐15 by treating the Ru complexes with SBA‐15 in benzene at room temperature. 1H NMR spectroscopy indicated that the reaction of complex 2 and [Ru(dtbpy)(CH2SiMe3)3(NO)] with SBA‐15 in C6D6 resulted in the formation of approximately 1 equiv. of SiMe4, which suggests the grafted species are possibly (≡SiO)Ru(tbtpy)(CH2SiMe3)(CO) and (≡SiO)Ru(dtbpy)(CH2SiMe3)2(NO), respectively. The Ru‐grafted SBA‐15 materials were characterized by IR, reflectance UV/Vis, and X‐ray photoelectron spectroscopy as well as transmission electronic microscopy, and their catalytic performance in the oxidation of benzyl alcohol with tert‐butyl hydroperoxide was examined.

Treatment of [Ir(dtbpy){CH2CMe2Cc6H4(Ir–Cc)}(C6H4tBu‐2)] (1) (dtbpy = 4,4′‐di‐tert‐butyl‐2,2′‐bipyridyl) with the dichalcogenides R2Q2 in refluxing toluene afforded the chalcogenolate‐bridged dinuclear complexes [Ir(dtbpy) {CH2CMe2Cc6H4(Ir–Cc)}]2(μ‐QR)2 [RQ = pTolS (2), PhSe (3)]. Similarly, heating a solution of [Rh(dtbpy){CH2CMe2Cc6H4(Ir–Cc)}(CH2CMe2Ph)] and p‐tolyl sulfide in toluene at reflux gave [Rh(dtbpy){CH2CMe2Cc6H4(Ir–Cc)}]2(μ‐SpTol)2 (4). Treatment of [Ir(dtbpy)(CH2CMe2Ph)Cl]2(μ‐Cl)2 with Na(Sxyl) (xyl = 2,6‐dimethylphenyl) and Na2(S∧S) afforded [Ir(dtbpy)(CH2CMe2Ph)(Sxyl)2]2 (5) and [Ir(dtbpy)(CH2CMe2Ph)(S∧S)]2 {S∧S2– = maleonitriledithiolate (6), toluene‐3,4‐dithiolate (7), benzene‐1,2‐dithiolate (8)}. Oxidation of compound 8 with AgOTf (OTf– = triflate) resulted in dimerization of the bdt2– ligand by S–S bond formation and the isolation of [Ir2(dtbpy)2(CH2Me2Ph)2{(bdt)2}][OTf]2 (9). The solid‐state structures of compounds 2, 3, 4, 7, and 9 were determined. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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