In metal carbonyls

Spectra and bonding in metal carbonyls part A, bonding. P. S. Braterman, Struct. Bonding (Berlin), 1972,10, 57-86 (110). 

Bradshaw AM, Cederbaum LS, Domcke W (1975) Ultraviolet Photoelectron Spectroscopy of Gases Adsorbed on Metal Surfaces. 24 133-170 Braterman PS (1972) Spectra and Bonding in Metal Carbonyls. Part A Bonding. 10 57-86 Braterman PS (1976) Spectra and Bonding in Metal Carbonyls. Part B Spectra and Their Interpretation. 26 1-42... 

An interesting study of the recoil behaviour of different nuclides in metal carbonyls was made by Harbottle and Zahn . They studied Cr(CO)6 and Mo(CO)g irradiated in various ways so as to produce nuclear reactions in oxygen and carbon, as well as both high and low energy reactions in Cr and Mo. The results can be briefly summarized as in Table 9. 

Braterman, P. S. In Metal Carbonyl Spectra Academic Press London, 1975, pp. 177-227. 

Nitrogen groups in metal carbonyls 84 and related complexes (471)... 

Nitrogen Groups in Metal Carbonyl and Related Complexes, 10, 115 Nitrosyls, 7, 211... 

N.m.r. studies are reported on the triethylphosphine and trisdi-methylaminophosphine complexes with boron halides, and triethylphos-phine complexes with aluminium chloride. A correlation of Sp with the number of phosphorus ligands in metal carbonyl complexes has led to a qualitative rationalization of 8p in terms of a- and 7r-bonding. ... 

Braterman, P. S. Spectra and Bonding in Metal Carbonyls. Part B Spectra and Their Interpretation. Vol. 26, pp. 1 2. 

Wade also extended the application of his rules to transition metal clusters the further extension by D. M. P. Mingos mainly concerns the bonding in metal carbonyl and metal phosphane clusters, i.e. organometallic compounds (Wade-Mingos rules) these are beyond the scope of this book. 

While the replacement of carbon monoxide by a tertiary phosphine ligand represents one of the most fundamental substitution reactions in metal carbonyl chemistry, it was not until 1975, some 16 years after the... 

The depressed reactivity of the CO bond in metal carbonyls relative to organic carbonyls is not apparent in the case of BH3 and A1H3. For example, Masters and coworkers have observed that I B THF reduces metal acyl compounds to the corresponding alkyls, eq. 16. Although no mechanistic studies have been reported, it... 

Protonation of the carbonyl oxygen is as yet only recognized in a couple of cases (34,35). Even though O-alkylation and perhaps 0-protonation open up useful synthetic paths in metal carbonyl chemistry, their main interest for the purposes of this survey is their intermediacy in the further reduction of CO. 

Base catalysis of ligand substitutional processes of metal carbonyl complexes in the presence of oxygen donor bases may be apportioned into two distinct classifications. The first category of reactions involves nucleophilic addition of oxygen bases at the carbon center in metal carbonyls with subsequent oxidation of CO to C02, eqns. 1 and 2 (l, 2). Secondly, there are... 

These observations illustrate that there are two transformations open to metallocarboxylic acid intermediates reversible loss of OH" accompanied by oxygen exchange, and metal-hydride formation with expulsion of C02. Our entry into this area of chemistry was in 1975 when extensive studies of oxygen lability in metal carbonyl cations were initiated (10). These... 

Figure 4.101 displays the subtle variations in metal-carbonyl bond lengths in the group 6 M(CO) complexes. In each case one can clearly distinguish the coordinate omc bonds (solid lines) from the hypervalent toMc prebonds (dashed lines). The latter are about 0.1A longer, but exhibit a similar vertical variation within the group. 

In many instances it is not necessary to isolate the acetonitrile complex or to carry out the reaction in acetonitrile. The use of amine oxide as a means of displacing carbonyl groups in metal carbonyls is well documented, and reaction proceeds smoothly with the carbonyl in the presence of a variety of ligands—e.g., ethylene or pyridine—to yield the monosubstituted derivatives. The advantage of the acetonitrile adducts is the stability of the compounds and the reactivity of the amine oxide toward acidic ligands. 

Table 12a. Standard enthalpy of formation, A/ff(g), enthalpy of disruption, AHjy, and metal-halogen bond enthalpy contribution, (M-X), in metal carbonyl halides (kJ mol-1)...

Z. Iqbal Intra- and Inter-Molecular Bonding and Structure of Inorganic Pseudohalides with Triatomic Groupings. P.S.Braterman Spectra and Bonding in Metal Carbonyls. Part A Bonding... 

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