Carbonyl ions

They have a signal from the carbonyl ion of carbamide, a signal that corresponds to ammonium ion, and a signal that characterizes the C-N bond. On the basis of the results obtained by us, only a rough scheme of cathode and anode reactions can be proposed because a number of bands in the IR spectra have not been identified ... 

This reaction takes place because of the ease of formation of the carbonylate ions and the favorable coordination of the Fe2+ produced. The reaction of Co2(CO)8 with NH3 is similar. 

A common method of preparing carbonylate ions is reduction of a neutral carbonyl complex. 

Carbonyl Hydride Acidification of carbonylate ions often results in the formation of carbonyl hydrido Complexes complexes, which may be regarded as the conjugate acids of the carbonylates ... 

Heck demonstrated Eq. (89) for a number of acylcobalt carbonyls, preparing them from the corresponding alkyl halide and sodium cobalt carbonylate. In the presence of bases, cobalt hydrocarbonyl regenerated cobalt carbonylate ion and a catalytic reaction resulted at atmospheric pressure and at temperatures from 0° to 100° C. Thus the following reaction was reported in 56% yield at 50° C ... 

A catalytic carboxyalkylation can also occur if the acylcobalt carbonyl is formed from an epoxide and sodium cobalt carbonylate ion. This reaction is discussed in Section II, D,l,a. 

Carbonylate Ions Numerous. miunic carbonyl complexes, aisti called caibtinylaic ions, are known. 

Carbonylate Ions NtimeixHis anionic carbonyl complexes, tdso called carbonylatc ions, are known. 

The syntheses of transition metal alkyls can be accomplished in several ways. A common approach is to take advantage of the nucleophilicity of a carbonylate ion.- For example ... 

The methodology for studying M-Ng complexes in the gas phase is essentially the same as the TRIR method for liquified noble gases a pump pulse photolyzes a metal carbonyl ion and the fragment is detected with the aid of a continuous IR laser. In these experiments helium is utilized as the standard buffer gas. A xenon complex may be detected by alteration in the spectrum and kinetics on addition of xenon. Since the spectra are free of solvent effects, the effect of coordination should be more easily discerned than in the liquid phase. This method has been used to study M(CO)sXe (M = Cr, Mo, W) and W(CO)sKr. Metal-xenon bond energies of ca. 35 kJmol are deduced from the kinetics of reaction with CO. The variation between metals in comparable to the error bars, about 4 kJ mol . The W-Kr bond energy is estimated to be less than 25 kJmol . ... 

The simpler carbonylate ions, like the binary carbonyls, obey the noble-gas formalism, and their stoichiometries can thus be predicted. The ions are usually fairly readily oxidized by air the alkali-metal salts are soluble in water, from which they can be precipitated by large cations such as [Co(NH3)6]3+ or [Ph4As]+. 

In addition to mononuclear carbonylate anions, a variety of polynuclear species have been obtained. The iron carbonylate ions, which have been much studied, are obtained by the action of aqueous alkali or Lewis bases on binary carbonyls or in other ways, for example,... 

The hydrides are not very soluble in water but in water they behave as acids, ionizing to give the carbonylate ions ... 

The CoNMR spectra of the tetrahedral [Co(PF3)4] and [Co(CO)4] anions have been recorded (191) and values obtained for the V( Co- P) (1222 25 Hz) and V( Co- C) (287 13 Hz) coupling constants. Approximate values for the cr-bond order were calculated and together with shift data suggested that bonding to the ligand tt orbitals is more important in the carbonylate ion than bonding to the phosphorus 3d orbitals of the tetrakis(trifluorophosphine)cobaltate, and that the cobalt-phosphorus u-bond order apparently is greater than the cobalt-carbon c7-bond order (191). 

The mechanism Is considered to Involve the charge-transfer state (MInorganic radical—for example, I, N3, and so on. Similarly, the rate constants of quenching of triplet eosln by anions In aqueous... 

Table II. Bond Dissociation Energies for Manganese Carbonyl Ions...

The sole study on transition metal carbonyl ion chemistry with ICR mass spectrometry has been published by Forster and Beauchamp 157), The ions produced by electron impact Fe+, Fe(CO)+ and Fe(CO)t in pure Fe(CO) 5, undergo two polymerization reactions to yield Fe CO)t and Fea(CO) 5. In binary mixtures with CHgF, H2O and NH3, substitution reactions occur like ... 

The branched products predominate in the reaction product. The reaction is a modified Reppe-Koch conversion. The copper carbonyl ion functions as a CO suppher, transporting the CO from the gas phase to the H2SO4 solution (Scheme 1.4). 

Metal carbonyl clusters, including Ir4(CO)i2, Irg(CO)i6, and Rh (CO),< , are adsorbed intact from alkane solution onto neutral supports such as Y-AI2O3 or TiOj. Adsorption on basic supports such as MgO or La203 causes formation of surface carbonylate ions such as [HIr4(CO),] and [IrgCCO) from It4(CO),2 and lr (CO),g, respectively. 

---