Spectroscopic properties and electronic structures of 17-electron half-sandwich ruthenium acetylide complexes, [Ru(CCAr)(L2)Cp′]+ (Ar=phenyl, p-tolyl, 1-naphthyl, 9-anthryl; L2=(PPh3)2, Cp′=Cp; L2=dppe; Cp′=Cp∗)

Some Ruthenium Derivatives of Penta-1,4-diyn-3-one

“…54 The model geometries were optimised at the B3LYP/3-21G* level of theory, [55][56][57][58][59] to reduce computational effort, with no symmetry constraints, in a manner similar to that reported elsewhere. 59 MOs and frequencies were computed on these optimised geometries at the same level of theory. All geometries were identified as minima (no imaginary frequencies).…”

The synthesis, molecular and electronic structure of cyanovinylidene complexes

“…The electrochemical response of ruthenium(II) acetylide complexes of general form Ru(CCAr)(PP)Cp' (Ar = aromatic substituent, PP = phosphine donors, Cp' = Cp, Cp*) is characterised by an oxidation event that has considerable ethynyl ligand character, and as such the potentials of these redox processes, and the chemical stability of the resulting radical cations, is sensitive to the nature of the aromatic group and the electronic properties of substituents [40,81]. However, the different combinations of solvent, supporting electrolyte, temperature and reference electrode employed in collecting the range of available data can make direct comparisons of the results collated from many different research groups difficult, especially in the absence of a reported potential for an internal reference compound [105].…”

“…However, the different combinations of solvent, supporting electrolyte, temperature and reference electrode employed in collecting the range of available data can make direct comparisons of the results collated from many different research groups difficult, especially in the absence of a reported potential for an internal reference compound [105]. Table 2 summarises the redox behaviour of a number of acetylide complexes pertinent to the present study in The cyclic voltammogram ( = 100 mV / s) of the parent compound Ru(CCPh)(PPh 3 ) 2 Cp (1) exhibits an oxidation wave at +0.54 V, which is only partially chemically reversible, even at -40C [40], as a result of the redox noninnocent nature of the phenylethynyl ligand and rapid dimerisation of the largely ligand-based radical cation in solution [106]. A completely irreversible wave is also observed at higher potentials (+1.34 V Table 2).…”

“…As a trade-off against the larger ligand sets, the relatively small 3-21G* basis set was employed with the B3LYP functional, although it should be noted that the 3-21G* basis set has proven to be sufficient to provide good agreement with experimental data in previous studies of half-sandwich ruthenium complexes [40]. The results of geometry optimisations are summarised in Table 3 [18] + ).…”

Syntheses, structures and redox properties of tris(pyrazolyl)borate-capped ruthenium vinyl complexes

“…It has now been firmly established that ruthenium alkynyl complexes Ru(CCR)(PP)Cp´ (P = phosphine, PP = bis(phosphine); Cp´ = Cp, Cp*) [13][14][15] and Ru(X)(CCR´´)(PP) 2 made progressively lower and lower in energy (e.g. 1-naphthyl, 9-anthryl, ethynylphenyl) [18][19][20], and when incorporated into bridging ligands spanning two strongly electron-donating ruthenium fragments [21][22][23][24][25][26][27][28]. 6 The complexes Ru(CH=CHR´´)(Cl)(CO)(PR 3 ) 2 L, which are readily prepared by insertion of an alkyne into the Ru-H bond in RuHCl(CO)(PR 3 ) n (n = 2, 3) [29] offer an entry point to a wide range of vinyl complexes through facile substitution reactions of the supporting phosphine and chloride ligands by a wide range of neutral and anionic mono and bidentate ligands (Scheme 1) [30,31].…”