Metal carbonyl species

It has generally been concluded that the photoinitiation of polymerization by the transition metal carbonyls/ halide system may occur by three routes (1) electron transfer to an organic halide with rupture of C—Cl bond, (2) electron transfer to a strong-attracting monomer such as C2F4, probably with scission of-bond, and (3) halogen atom transfer from monomer molecule or solvent to a photoexcited metal carbonyl species. Of these, (1) is the most frequently encountered. 

In addition, hydrogen bonding was still observed at 3,583 cm (Fig.l A). IR peaks in VC.O region (Fig.l B) shifted to lower frequency after adsorption due to precursor-support interaction and differed from that of cluster solution implying that precursor was not intact after adsorption on support but still in the form of metal carbonyl species. 

Weitz and co-workers extended gas phase TRIR investigations to the study of coordinatively unsaturated metal carbonyl species. Metal carbonyls are ideally suited for TRIR studies owing to their very strong IR chromophores. Indeed, initial TRIR work in solution, beginning in the early 1980s, focused on the photochemistry of metal carbonyls for just this reason. Since that time, instrumental advances have significantly broadened the scope of TRIR methods and as a result the excited state structure and photoreactivity of organometallic complexes in solution have been well studied from the microsecond to picosecond time scale. ... 

These reactions had similar rate constants, 4 x 109 dm3 mol-1 second-1, which approached the diffusion-controlled limit. Thus, for 10-2 M concentration of added ligand the half-life of Cr(CO)5 would be 17 nseconds. Interest in these experiments has been reawakened by the recent reports of photoactivation of alkanes by metal carbonyl species 34). 

Flash photolysis has now been applied to a wide range of metal carbonyl species in solution, including Mn2(CO)10 (37), [CpFe(CO)2]2 (38), and [CpMo(CO)3]2 (39). In almost every case, interesting data have emerged, but, as with Cr(CO)5, the structural information is usually minimal. Thus, the radical Mn(CO)5 has been generated in solution by flash photolysis (37), the rate constant for its bimolecular recombination has been measured, but the experiments did not show whether it had Z>3h or Qv symmetry. Some experiments have been unsuccessful. Although the fragment Fe(CO)4 is well known in matrices (15), it has never been... 

Already a considerable number of transient organometallic species have been characterized by IR kinetic spectroscopy (see Table I). Like most other sporting techniques for structure determination, IR kinetic spectroscopy will not always provide a complete solution to every problem. What it can do is to provide more structural information, about metal carbonyl species at least, than conventional uv-visible flash photolysis. This structural information is obtained without loss of kinetic data, which can even be more precise than data from the corresponding uv-visible... 

Nevertheless, we were able to develop a transient absorption apparatus involving IR probe radiation that is suitable for gas phase studies, as have a number of other groups either coincident with or subsequent to our work [1]. In the remainder of this article we will discuss the apparatus and the results of our studies on three prototypical metal carbonyl species Fe(C0>5, Cr(C0>5 and Mn2(CO)] o The discussion in this article will center on the nature of the photolytically generated coordinatively unsaturated species, their kinetic behavior and photophysical information regarding these species. This latter information has enabled us to comment on the mechanism for photodissociation in these systems. Since most of the results that will be discussed have been presented elsewhere [3-10], we will concentrate on a presentation of data that illustrates the most important features that have come out of our research and directly related research regarding the kinetics, photophysics and photochemistry of coordinatively unsaturated metal carbonyls. 

A further point of interest is their ready interconversion in solution, which we have studied by variable temperature n.m.r. measurements (8). Reaction of [(n-C5H5)(0C)2W =CR] with polynuclear metal carbonyl species is likely to afford many new heteronuclear cluster compounds containing tungsten. 

We have exploited this base catalysis of the oxygen exchange process to effect oxygen lability in the less electrophilic carbonyl sites of neutral metal carbonyl species. Because [MCOOH] intermediates are readily decarboxylated in the presence of excess hydroxide ion, in order to observe oxygen exchange processes in neutral metal carbonyl complexes it was convenient to carry out these reactions in a biphasic system employing phase transfer catalysis () (16, 17. 18). Under conditions (eq. 7) the... 

Braunstein, P., Dehand, J. Chem. Metal-metal IR frequencies etc. in a variety of Comms. 1972, 164 metal carbonyl species... 

As indicated in Chapter 8, the production of alkanes, as by-products, frequently accompanies the two-phase metal carbonyl promoted carbonylation of haloalkanes. In the case of the cobalt carbonyl mediated reactions, it has been assumed that both the reductive dehalogenation reactions and the carbonylation reactions proceed via a common initial nucleophilic substitution reaction and that a base-catalysed anionic (or radical) cleavage of the metal-alkyl bond is in competition with the carbonylation step [l]. Although such a mechanism is not entirely satisfactory, there is no evidence for any other intermediate metal carbonyl species. 

Further evidence for the intermediacy of an -vinylcarbene has been provided by Garcia-Mellado and Alvarez-Toledano.139 They have shown that lithium dimethylcuprate may be used in place of an alkyllithium reagent in the absence of carbon monoxide, necessary CO being scavenged from other metal-carbonyl species hence the low yields observed from these reactions. 

The effective path length with the TIR cell is much shorter and composition information can be abstracted from the fingerprint region as well as direct observation of metal carbonyl species and CO2. However, the shorter path length can make detection and quantification of low concentrations of catalyst species more difficult. 

As well as characterizing complexes involved in the main catalyst cycles, spectroscopy has contributed to the measurement of the kinetics of these cycles and to byproduct reactions. The major catalyst species present under working conditions of the catalyst systems have been identified for all the systems. Individual reaction steps involving interconversion of catalyst complexes have been isolated and studied in model reactions. IR has been very important in these studies with metal carbonyl species, including the identification of Ru promoter species in MeOH carbonylation. 

In a more detailed examination of the ruthenium-cobalt-iodide "melt" catalyst system, we have followed the generation of acetic acid and its acetate esters as a function of catalyst composition and certain operating parameters, and examined the spectral properties of these reaction products, particularly with regard to the presence of identifiable metal carbonyl species. 

One of the most remarkable recent advances in metal carbonyl substitution chemistry has been the discovery by Coville and co-workers of the homogeneous and heterogeneous catalytic labilization of the metal-carbon bond in metal-carbonyl complexes (26-31). Considering that restrictions to catalysis involving metal carbonyl species can, in some instances, be related to the strength of the metal-carbon bond, these discoveries could have far-reaching implications. To exemplify these catalytic substitution processes, comparisons in the systems M(CO)6(M = Cr, Mo, W), CpMoI(CO)3, CpFeI(CO)2, Fe(CO)5, Fe(CO)4(olefin), and Ir4(CO)12 will be made. 

The reaction of binuclear metal carbonyls with bases has been recognized (137, 229, 244) as producing cationic metal carbonyl species, although the earlier derivatives defied isolation. This has been classed as a base reaction (122). 

Spectral resolution and transient IR tests of this instrument were conducted using metal-carbonyl species dissolved in n-hexane. These... 

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