Facile and systematic access to the least-coordinating WCA [(RO)Al-F-Al(OR)] and its more Lewis-basic brother [F-Al(OR)] (R = C(CF)).

By reaction of the Lewis acid MeSi-F-Al(OR) with a series of [PF] salts, gaseous PF and MeSi-F are liberated and salts of the anion [F-Al(OR)] ([f-al]; R = C(CF)) can be obtained. By addition of another equivalent of MeSi-F-Al(OR) to [f-al], gaseous MeSi-F is released and salts of the least coordinating anion [(RO)Al-F-Al(OR)] ([al-f-al]) are formed. Both procedures work for a series of synthetically useful cations including Ag, [NO], [PhC] and in very clean reactions with 5 g batch sizes giving excellent yields typically exceeding 90%.

How does the Environment Influence a Given Cation? A Systematic Investigation of [Co(CO) ] in Gas Phase, Solution, and Solid State.

IR spectroscopic studies of the gaseous metal carbonyl cations [Co(CO) ] ⋅mCO (m=1-4) indicated that the weakly bound CO molecules in a second coordination sphere perturb the structure of [Co(CO) ] causing the CO stretching frequencies ν(CO) to become noticeably redshifted. In this work, we aimed to establish the relationship between such gas phase IR spectra and those recorded in condensed phases, either as a solid salt or as a solution in the weakly basic solvent o-difluorobenzene. For this purpose, a series of [Co(CO) ] [WCA] salts (WCA=weakly coordinating anion), with the counterions varying between more coordinating (WCA=F-Al(OR ) , (R O) Al-F-Al(F)(OR ) ; R =C(CF ) ) and almost non-coordinating (WCA=Al(OR ) , F{Al(OR ) } ), were synthesized and characterized by vibrational spectroscopy as well as X-ray structure analysis.

Access to the Bis-benzene Cobalt(I) Sandwich Cation and its Derivatives: Synthons for a "Naked" Cobalt(I) Source?

The synthesis and structural characterization of the hitherto unknown parent Co(bz) (bz=benzene) complex and several of its derivatives are described. Their synthesis starts either from a CoCO salt, or directly from Co (CO) and a Ag salt. Stability and solubility of these complexes was achieved by using the weakly coordinating anions (WCAs) [Al(OR ) ] and [F{Al(OR ) } ] {R =C(CF ) } and the solvent ortho-difluorobenzene (o-DFB).

From an Easily Accessible Pentacarbonylcobalt(I) Salt to Piano-Stool Cations [(arene)Co(CO) ].

The facile synthesis of a pentacarbonyl cobalt(I) salt without the need for a superacid as solvent is presented. This salt, [Co(CO) ] [Al(OR ) ] {R =C(CF ) }, readily accessible on a multigram scale, undergoes substitution reactions with arenes yielding the hitherto unknown class of two-legged cobalt piano-stool complexes [(arene)Co(CO) ] with four different arene ligands. Such a substitution chemistry would have been impossible in superacid solution, as the arenes used would have been oxidized and/or protonated.

Sticking and patching: tuning and anchoring cyclometallated ruthenium(II) complexes.

A series of [Ru(bpy)2(C^N)][PF6] (HC^N = 2-phenylpyridine derivative) complexes functionalized in the cyclometallating C^N phenyl ring with F, Me, OMe, CO2Me, S(t)Bu, SO2Me (ligands H1-H6) or in the C^N pyridine ring with 4-CO2Me or 4-C6H4P(O)(OEt)2 substituents (ligands H7 or H9) have been prepared and characterized; representative crystal structures confirm the structural features of the complexes. When the C^N ligand contains a CO2H substituent (ligand H28), deprotonation in addition to cyclometallation occurs to give a neutral, zwitter-ionic complex [Ru(bpy)2(8)]. The synthesis of the cationic complexes requires addition of a silver(i) salt (AgPF6 or AgBF4) to abstract Cl(-) from cis-[Ru(bpy)2Cl2] and (1)H NMR spectroscopic data are consistent with interactions between Ag(+) and the coordinated C^N ligand in [Ru(bpy)2(C^N)](+).