Hexacarbonyl bonding

The neutral complexes of chromium, molybdenum, tungsten, and vanadium are six-coordinate and the CO molecules are arranged about the metal in an octahedral configuration as shown in stmcture (3). Vanadium carbonyl possesses an unpaired electron and would be expected to form a metal—metal bond. Steric hindrance may prevent dimerization. The other hexacarbonyls are diamagnetic. 

CBS extrapolation 155, 278 CBS methods 10, 96, 155 cost vs. G2 methods 159 CBS-4 method 155 CBS-Q method 155 CCSD keywords 114 CH bond dissociation 186 charge xxxv, xlii, 15, 286 predicted atomic li charge distribution 20 Cheeseman 53 chlorine (atomic) 137, 159 chlorobenzene 165 chromium hexacarbonyl 52 Cioslowski 198 CIS keyword... 

Compounds containing M-C cr-bonds are frequently unstable and do not give rise to an extensive chemistry (p. 999). Vanadium forms a neutral (paramagnetic) hexacarbonyl which, though not very stable, contrasts with that of titanium in that it can at least be prepared in... 

The rapid first-order exchange rate ° for Ni(CO)4 is to be contrasted with the much slower rates for the carbonylate anions Co(CO)4 and Fe(CO)4 , and this is quite in accordance with a higher M-C bond order in these two latter compounds, provided that the primary reaction step is a dissociative one. The group VI hexacarbonyls exchange CO several orders of magnitude more slowly than Ni(C0)4 by a first-order process in the gas phase There is very good... 

The same first-order replacements are seen when M is Mo or W, somewhat slower than in the case of Cr, but still much faster than for the hexacarbonyls. The rate increases with the pK of the inert ligand (N-N) and Fig. 9 shows the linear free-energy relation between log ki and pK . The relative orders would not have been expected on the basis of any 7t-bonding effects since increasing back-donation to CO would increase the M-C bond order. This increase in M-C bond order is supported by a decrease in Vco with increasing o-phenanthroline basicity. The same consideration applies for the pentacarbonyl halide anions where the first-order rates decrease (Cl > Br > I), unexpectedly as the halide polarizability increases. 

Table 8-6. Bond lengths for neutral hexacarbonyl complexes of Cr, Mo, and W in Oh symmetry [A],...

The formation of 2H-pyrroles (21) and a pyrrole derivative (22) from the reaction of 3-phenyl-2//-azirines and acetylenic esters in the presence of molybdenum hexacarbonyl is intriguing mechanistically (Schemes 24, 25).53 Carbon-nitrogen bond cleavage must occur perhaps via a molybdenum complex (cf. 23 in Scheme 26) but intermediate organometallic species have not yet been isolated.53 Despite the relatively poor yields of 2H-pyrrole products, the process is synthetically valuable since the equivalent uncatalyzed photochemical process produces isomeric 2H-pyrroles from a primary reaction of azirine C—C cleavage54 (Scheme 24). 

Scheme 22 illustrates a special application of the azide-tetrazole ring closure described by Ponticelli et al. <2004JHC761>. The diazido compound 84 exists as an azide valence bond isomer. When this compound, however, is subjected to reduction by molybdenum hexacarbonyl, one azido group undergoes reduction selectively to an... 

Sulfoxide adducts of chromium, molybdenum, and tungsten carbonyls have been studied as catalysts for the polymerization of monomers such as vinyl chloride (248). Simple adducts of the type [M(CO)5(Me2SO)] may be prepared by carbonyl displacement from the corresponding hexacarbonyl. Photochemical reactions are frequently necessary to cause carbonyl displacement in this manner, many carbonyl complexes of higher sulfoxides have been prepared (255, 256). Infrared (257) and mass spectral studies (154) of these complexes have appeared, and infrared data suggest that S-bonding may occur in Cr(0) sulfoxide complexes, although definitive studies have not been reported. 

To derive the chromium-benzene bond dissociation enthalpy, the values of several stepwise bond dissociation enthalpies in chromium hexacarbonyl are... 

Although we ignore the values for some of the six stepwise Cr-CO bond dissociation enthalpies in chromium hexacarbonyl, their sum is equal (equation 5.16) to the enthalpy of reaction 5.15, which is calculated as 641.7 4.8 kJ mol-1 (at 298.15 K) from the well-known standard enthalpies of formation of all the species involved [16,17,31],... 

The heat of formation of [MolCOlg] has been determined as -960 + 12 kJ mol by measuring its heat of decomposition. The Mossbauer parameters for the 100 keV transition of in [W(CO)g] and some tungsten(vi) complexes have been measured and discussed in terms of known bonding and structure. Secondary ions [M (CO) ] (M = Mo, m = I or 2 M = W, m = 1—4 n = 0—14) formed by ion-molecule reactions have been observed in the mass spectra of the hexacarbonyls. A mixt u re of [Cr(CO) ] and [MolCO) ] vapours affords [CrMo(CO) ] ( = 5—7). [MofCOl ] and [WICO) ] catalyse the condensation of isocyanates with aldehydes to give imines in high yields. ... 

Dicyclopentadienyldinickeldiphenylbutadiyne-dicobalt hexacarbonyl has been prepared from diphenyldiacetylene in which one triple bond acts as a bridging group between two nickel atoms and the other between two cobalt atoms (203). Reduction of the diphenylacetylene complex (R = R = Ph) with sodium and alcohol in liquid ammonia yields dibenzyl, showing that the diphenylacetylene grouping is bonded only to the nickel atoms. The corresponding complex of acetylene (R = R = H) has also been prepared from nickeloccne and acetylene (69) ... 

The molybdenum(II) carboxylates, Mo2(02CR)4, are key derivatives containing molybdenum-molybdenum quadruple bonds.1 First described by Wilkinson and coworkers in the early 1960s,2 they remain the key starting materials in (Mo2)4 + chemistry and they have been the objects of numerous physical and theoretical studies.1 The most commonly used method of preparation is the reaction between molybdenum hexacarbonyl and a carboxylic acid in an inert solvent such as 1,2-dichlorobenzene (DCB) [eq. (I)].3 Excellent yields of Mo2(02CR)4 can be obtained by... 

Many complexes of conjugated ketones are also known, such as the iron tricarbonyl complexes of substituted cyclopentadienones 30), although reaction with chromium hexacarbonyl occurs only if phenyl substituents are available for tt complexing 31). A common difficulty of preparing complexes of heterocyclics is the ability of the heteroatom to form o bonds with the metal. 

Kinetics. The kinetics of the epoxidation of olefins with tert-butyl hydroperoxide in the presence of molybdenum hexacarbonyl have been studied. The reaction rate is first order in tert-butyl hydroperoxide, in olefin, and in molybdenum hexacarbonyl. Olefins substituted near the double bond by electron-releasing alkyl groups react more rapidly than the corresponding unsubstituted olefins. The kinetic data indicate that the epoxidation reaction proceeds according to the rate law,... 

The molecule of diphenylacetylene dicobalt hexacarbonyl has been shown by an x-ray investigation.57 to have the structure shown in Figure 11-19. Each cobalt atom forms six bonds, directed toward the corners... 

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