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[Ru(VI)(TMP)(NSO2R)2] (SO2R = Ms, Ts, Bs, Cs, Ns; R = p-C6H4OMe, p-C6H4Me, C6H5, p-C6H4Cl, p-C6H4NO2, respectively) and [Ru(VI)(Por)(NTs)2] (Por = 2,6-Cl2TPP, F20-TPP) were prepared by the reactions of [Ru(II)(Por)(CO)] with PhI=NSO2R in CH2Cl2. These complexes exhibit reversible Ru(VI/V) couple with E(1/2) = -0.41 to -0.12 V vs Cp2Fe(+/0) and undergo imido transfer reactions with styrenes, norbornene, cis-cyclooctene, indene, ethylbenzenes, cumene, 9,10-dihydroanthracene, xanthene, cyclohexene, toluene, and tetrahydrofuran to afford aziridines or amides in up to 85% yields. The second-order rate constants (k2) of the aziridination/amidation reactions at 298 K were determined to be (2.6 +/- 0.1) x 10(-5) to 14.4 +/- 0.6 dm3 mol(-1) s(-1), which generally increase with increasing Ru(VI/V) reduction potential of the imido complexes and decreasing C-H bond dissociation energy (BDE) of the hydrocarbons. A linear correlation was observed between log k' (k' is the k2 value divided by the number of reactive hydrogens) and BDE and between log k2 and E(1/2)(Ru(VI/V)); the linearity in the former case supports a H-atom abstraction mechanism. The amidation by [Ru(VI)(TMP)(NNs)2] reverses the thermodynamic reactivity order cumene > ethylbenzene/toluene, with k'(tertiary C-H)/k'(secondary C-H) = 0.2 and k'(tertiary C-H)/k'(primary C-H) = 0.8.

Ruthenium porphyrins constitute an unmatched family of metalloporphyrin that exhibits extraordinary versatility in binding N-donating ligands at the axial sites. [1±5] A wide variety of ruthenium porphyrins featuring axial RuÀN bonds have been prepared, including those bearing amine, [1c, 3a,3b] amido, [3b±d,g] imido, [3a,c±e,g,j] imine, [3h, 4] methyleneamido, [3h] nitrile, [1a, 2] hydrazido, [3f] nitrosoarene, [1b, 3i] nitrosyl, [5] and dinitrogen [1d] axial ligands (Scheme 1, a±j). This makes the lack of [*] Prof.

Treatment of [Cu2(dcpm)2]Y2 (dcpm = bis(dicyclohexylphosphino)methane, Y = ClO4-, BF4-, PF6-, CF3SO3-) with refluxing MeOH in the presence of KOH afforded hydride complexes [Cu3(dcpm)3(mu3-H)]Y2 (1) in about 85% yield. Refluxing [Cu2(dcpm)2](PF6)2 with MeOH in the presence of NH3.H2O and air gave a carboxylate complex [Cu2(dcpm)2(O2CCH2OH)]PF6 (2) in 40% yield. All of the complexes 1 and 2 have been characterized by X-ray crystallography. The Cu3 cores in 1 are almost perfectly shielded by the dcpm ligands. Intense photoluminescence was observed for 1 both in the solid state and in solution.

Reaction of dioxoruthenium(VI) porphyrins [Ru(VI)(Por)O2] with arylimine HN=CPh2 in dichloromethane afforded bis(methyleneamido)ruthenium(IV) porphyrins [Ru(IV)(Por)(N=CPh2)2] for Por = 4-Cl-TPP and TMP; (methyleneamido)hydroxoruthenium(IV) porphyrins [Ru(IV)(Por)(N=CPh2)(OH)] for Por = TPP and TTP; and bis(arylimine)ruthenium(II) porphyrins [Ru(II)(Por)(HN=CPh2)2] for Por = 3,5-Cl2TPP and 3,5-(CF3)2TPP. In dichloromethane solution exposed to air, complex [Ru(II)(3,5-Cl2TPP)(HN=CPh2)2] underwent oxidative deprotonation to form [Ru(IV)(3,5-Cl2TPP)(N=CPh2)2]. The new ruthenium porphyrins were identified by 1H NMR, UV-vis, IR, and mass spectroscopy, along with elemental analysis. X-ray crystal structure determinations of [Ru(IV)(4-Cl-TPP)(N=CPh2)2], [Ru(IV)(TPP)(N=CPh2)(OH)], and [Ru(II)(3,5-(CF3)2TPP)(HN=CPh2)2] revealed the Ru-N(methyleneamido) or Ru-N(arylimine) distances of 1.897(5) A (average), 1.808(4) A, and 2.044(2) A (average), respectively.

Ruthenium porphyrins constitute an unmatched family of metalloporphyrin that exhibits extraordinary versatility in binding N-donating ligands at the axial sites. [1±5] A wide variety of ruthenium porphyrins featuring axial RuÀN bonds have been prepared, including those bearing amine, [1c, 3a,3b] amido, [3b±d,g] imido, [3a,c±e,g,j] imine, [3h, 4] methyleneamido, [3h] nitrile, [1a, 2] hydrazido, [3f] nitrosoarene, [1b, 3i] nitrosyl, [5] and dinitrogen [1d] axial ligands (Scheme 1, a±j). This makes the lack of [*] Prof.

Bis(N-ethylideneethanamine)ruthenium(ii) porphyrins, [Ru11(Por)(N(Et)=CHMe)2] (Por=TTP, 4-Cl-TPP), were prepared by the reaction of dioxoruthenium(VI) porphyrins with triethylamine in approximately 85% yields. The reaction between dioxoruthenium(VI) porphyrins and benzophenone imine afforded bis(diphenylmethyleneamido)ruthenium(IV) porphyrins, [Ru(IV)(Por)(N=CPh2)2] (Por=TTP, 3,4,5-MeO-TPP), in approximately 65% yields. These new classes of metalloporphyrins were characterized by 1H NMR, UV/Vis, and IR spectroscopy as well as by mass spectrometry and elemental analysis. The X-ray crystallographic structures of [Ru(II)(TTP)(N(Et)=CHMe)2] and [Ru(IV)(3,4,5-MeO-TPP)(N=CPh2)2] revealed an axial Ru-N bond length of 2.115(6) A for the imine complex and 1.896(8) A for the methyleneamido complex. Each of the N=CPh2 axial groups in [Ru(IV)(3,4,5-MeO-TPP)(N=CPh2)2] adopts a linear coordination mode with a corresponding Ru-N-C angle of 175.9(9)degrees. Spectral and structural studies revealed essentially single bonding character for the bis(imine) complexes but a multiple bonding character for the bis(methyleneamido) complexes with respect to their axial Ru-N bonds.

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