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The linear bis-cyclometalated Ru(II) complex [(ttpy)Ru(ttabp)Ru(ttpy)]2+was prepared from the oxidative coupling of the monometalliccomplex [(ttpy)Ru(dtab)]+in good yield, where ttpy is4′-tolyl-2,2′:6′,2″-terpyridine, ttabpis 3,3′,5,5′-tetrakis(1-butyl-1H-1,2,3-triazol-4-yl)biphenyl,and dtab is 1,3-bis(1-butyl-1H-1,2,3-triazol-4-yl)benzene.The electronic properties of these two complexes were studied andcompared by electrochemical and spectroscopic methods and DFT/TDDFTcalculations. The complex [(ttpy)Ru(ttabp)Ru(ttpy)]2+showedtwo consecutive RuII/IIIredox waves at +0.34 and +0.51V vs Ag/AgCl with a comproportionation constant Kcof 760. One-electron oxidation of [(ttpy)Ru(ttabp)Ru(ttpy)]2+by electrochemical methods produced the mixed-valent complex[(ttpy)Ru(ttabp)Ru(ttpy)]3+, which exhibited a symmetricintervalence charge transfer band at 1800 nm (νmax= 5550 cm–1, εmax= 5100 M–1cm–1, Δν1/2= 3580 cm–1). The energy and shape of this bandare very similar in the different solvents studied (CH3CN, DMF, CH2Cl2). [(ttpy)Ru(ttabp)Ru(ttpy)]3+was determined to be a class II/III borderline system withthe electronic coupling parameter Hab=530 cm–1. It displayed a metal-centered rhombicEPR signal at 77 K with an isotropic gfactor of2.109 and total ganisotropy of 0.256, which pointsto an appreciable spin distribution on the bridging ligand in additionto the metal centers. [ABSTRACT FROM AUTHOR]

A new bridging ligand 1,3,6,8-tetrakis(1-butyl-1H-1,2,3-triazol-4-yl)pyrene (ttapyr) was designed and synthesized by "click" chemistry. This ligand was used to construct a linear dimetallic biscyclometalated Ru(II) complex [(tpy)Ru(ttapyr)Ru(tpy)]2+ and a monometallic complex [(tpy)Ru(ttapyr)]+, where tpy is 2,2′:62′,22″-terpyridine. The electronic properties of these complexes were studied and compared by electrochemical and spectroscopic methods with the aid of DFT calculations. One-electron oxidation of [(tpy)Ru(ttapyr)Ru(tpy)]2+ with cerium ammonium nitrate produced a mixed-valent complex [(tpy)Ru(ttapyr)Ru(tpy)]3+. The intramolecular electronic coupling between individual metal centers was quantified by the intervalence charge transfer transition analysis. Mixed-valent complex [(tpy)Ru(ttapyr)Ru(tpy)]3+ exhibits a metal-centered rhombic EPR signal at 77 K with an average g factor of 2.203. [ABSTRACT FROM AUTHOR]

A tridentate cyclometalating ligand, 1,3-di(1,2,3-triazol-4-yl)benzene (dtab), has been prepared and used for the syntheses of a number of cyclometalated RuIIcomplexes. A comparison of the electrochemical and spectroscopic properties of cyclometalated complexes made from dtab or 1,3-di(2-pyridyl)benzene is presented as well. [ABSTRACT FROM AUTHOR]

Cyclometalated diruthenium complexes 1(PF6)2–5(PF6)2 bridged by 1,3,6,8-tetra(pyrid-2-yl)-pyrene have been prepared, with the terminal ligand bis(N-methylbenzimidazolyl)pyridine (1(PF6)2), 4′-di-(p-methoxyphenyl)amino-2,2′:6′,2″-terpyridine (2(PF6)2), 4′-p-methoxyphenyl-2,2′:6′,2″-terpyridine (3(PF6)2), 2,2′:6′,2″-terpyridine (4(PF6)2), and trimethyl-4,4′,4″-tricarboxylate-2,2′:6′,2″-terpyridine (5(PF6)2). The single-crystal X-ray structure of 4(PF6)2 is presented. These complexes show two stepwise anodic redox pairs, and the potentials progressively increase from 1(PF6)2 to 5(PF6)2. Complexes 1(PF6)2–4(PF6)2 have comparable electrochemical potential splitting of 200–210 mV, while complex 5(PF6)2 has a splitting of 170 mV. Upon one-electron oxidation by chemical oxidation or electrolysis, the resulting mixed-valent complexes 13+–53+ display broad and intense absorptions between 1000 and 3000 nm. Complexes 13+ and 23+ show the presence of a higher-energy shoulder band in addition to the main near-infrared absorption band. This shoulder band is less distinguished for 33+–53+. Three-state theory has been used to explain this difference. The one-electron oxidized forms, 13+–53+, exhibit rhombic EPR signals at 77 K with the isotropic g values in the range of 2.18–2.24. Density functional theory (DFT) and time-dependent DFT (TDDFT) computations have been performed on 12+–52+ to characterize their electronic structures and rationalize the absorption spectra in a wide energy range. DFT computations on 13+–53+ show that both ruthenium ions and the bridging ligand have comparable spin densities. TDDFT computations on 13+ and 43+ have been performed to complement the experimental results. [ABSTRACT FROM AUTHOR]

Gas-phase cyclometalation of [ArNi(PPh3) n ]+ (n = 1, 2) complexes have been studied by ESI-MS/MS. The electron-donating substituents of aromatic iodides in the para position were found to inhibit the cyclometalation process of losing ArH, while the electron-withdrawing substituents in the para position were found to enhance it. These results indicate that the cyclometalation process of losing ArH is favored by electron-deficient aromatic groups. In addition, the detailed dissociation pathways of the cationic nickel complexes were studied, and among these pathways, the process of aryl-aryl interchange was also found to proceed in ESI-MS/MS. [Copyright &y& Elsevier]