Carbonyl complexes dissociation

Relatively few investigations involving palladium carbonyl clusters have been carried out, partly because palladium per se does not form stable, discrete homometallic carbonyl clusters at room temperature in either solid or solution states.114,917-922 Nevertheless, solution-phase palladium carbonyl complexes have been synthesized with other stabilizing ligands (e.g., phosphines),105,923 and carbon monoxide readily absorbs on palladium surfaces.924 Moreover, gas-phase [Pd3(CO)n]-anions (n = 1-6) have been generated and their binding energies determined via the collision-induced dissociation method.925... 

Treatment of 4 with either PF3 or 13CO results in CO substitution believed to proceed via a dissociative process yielding Ti(CO)2(PF3)-(dmpe)2 (6) and Ti(13CO)3(dmpe)2. Structural characterization of 6 showed it also to be monomeric, but possessing a monocapped trigonal prismatic geometry. Complexes 4, 5, and 6 may be considered phosphine-substituted derivatives of the as yet unisolated Ti(CO)7, thus representing the only isolable titanium carbonyl complexes where the titanium atom is in the zero oxidation state. 

Unlike hydrogen these reactions do not appear to be activated. In addition the products distributions observed indicate comparable rates for multiple adduct formation. The mass complexity, relatively high ionization potentials, and the known prevalent dissociative ionization of the fully saturated carbonyls(42) has possibly caused the failure of some initial saturation experi ments(43). The ability to synthesize the stable carbonyl complexes will help this field significantly due to the vast amount of information available, especially their structures. 

Pensak and McKinney (28) [PM], using this method, have recently reported a systematic study of first-row transition metal carbonyl complexes for which experimental bond distances and angles were reliably reproduced, along with key bond dissociation energies. 

Kinetic studies of the substitution reaction of (CO)3M[ 3-C3(t-Bu)3] (M = Co, Rh, Ir) with P(OEt)3 provide the first examples of dissociative CO substitution for carbonyl complexes of the cobalt triad (equation 256)323. 

C-H bond dissociation energies, 1, 298 C-N triple bond additions, 10, 427 C02, ketene, ketenimine complexes, 5, 84 CO and CNR reductive coupling, 5, 66 cyclopentadienyl alkyl and aryls, 5, 66 cyclopentadienyl carbonyl complexes, 5, 64 cyclopentadienyl hydrides, 5, 69 cyclopentadienyl isocyanide complexes, 5, 65 rf-acyl and rj2-iminoacyl complexes, 5, 82 fj3-complexes, 5, 87... 

Table 1 DFT-calculated M-NHC bond dissociation energies (kcalmol 1) and °/oVbut f°r the carbene ligands in nickel-carbonyl complexes ...

Imhof et al. [22] studied the reaction mechanism of the [2+2+1] cycloaddition reactions of diimines, CO, and ethylene catalyzed by iron carbonyl complexes on the basis of density functional theory (Scheme 4). The catalytic reaction does not start when CO dissociates from 10 followed by the addition of ethylene, but instead the associative pathway to 11 is proposed. In addition, it can be concluded that the insertion of CO in 11 takes place into a C-Fe bond but not... 

The primary photochemical reaction of the [MM (CO)i0] (M, M =Mn, Re) complexes in solution has been shown to result in (1) homolytic fission of the metal-metal cr-bond to form M(CO)s radicals, (2) dissociation of a CO ligand to form [MM (CO)9], and (3) non-dissociative relaxation to the electronic ground state [86]. Similar behaviour is shown by other dinuclear carbonyl complexes [87]. 

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