Ring closure following flash photolysis in alkane solvents has been detected for several complexes in the series (η5-C5H4R)Mn(CO)3 where R = COCH3 (1), COCH2SCH3 (2), CO(CH2)2SCH3 (3), COCH2OCH3 (4), (CH2)2CO2CH3 (5), and CH2CO2CH3 (6). In each case where ring closure occurs, a metal CO is ultimately substituted by the side chain functional group. Photoacoustic calorimetry studies reveal that ring closures occur with rate constants faster than 107 s-1 or between 106 and 107 s-1, or in some cases the ring closure is biphasic with rate constants in both ranges. The enthalpies of CO dissociation followed by ring closure for 2 and 3 are the same (12 kcal/mol) and more favorable than those for 4−6 (25−15 kcal/mol). Studies of 1−3 by transient picosecond to microsecond infrared spectroscopy confirm biphasic dynamics for 2 and 3: ring closure occurs immediately (k > 5 × 109 s-1) and at slower rates (k = 108−106 s-1). We propose that some ring closure occurs before solvent coordination and that the remaining ring closure, resulting in the displacement of solvent, is much slower. The relationships of the rates and energetics of ring closure to structure and quantum yields are discussed.
Photoacoustic calorimetry (PAC) and actinometry studies were used to determine the enthalpies and volumes of reaction for the production of a transient intermediate, Mo(CO)(5)-alkane, and for its subsequent reaction with tetrahydrofuran (THF). Both the enthalpy and the volume of reaction contribute to the photoacoustic signal and have been resolved by changing the solvent thermal expansion properties with a series of linear alkanes. The enthalpies for substitution of CO on Mo(CO)(6) by an alkane and of coordinated alkane on Mo(CO)(5)(alkane) by THF are 30 and -14 kcal/mol, respectively. Likewise, the volumes of reaction are 18 and -1 mL/mol. From available data for the Mo--CO bond energy, these results allow the calculation of the Mo-alkane and Mo-THF bond energies (11 and 25 kcal/mol, respectively). The Mo-alkane result is 7 kcal/mol less than that from our previous PAC study, which ignored the volume of reaction, and is in better agreement with the results of kinetic studies. The large absolute difference in the reaction volumes for each step is partially attributed to a void volume created during the formation of the Mo--THF bond. In general, the volume of reaction cannot be neglected in the calculation of enthalpies of ligand substitution from PAC studies. The quantum yields for photosubstitution of Mo(CO)(6), in contrast to Cr(CO)(6), were found to be insensitive to the chain length of the alkane solvent.
The photosubstitution reactions of molybdenum hexacarbonyl with σ and π donor ligands were investigated using photoacoustic calorimetry and computational methods in a series of linear alkane solvents (pentane, hexane, heptane, octane, decane, and dodecane). The results show that reaction volumes make a significant contribution to the photoacoustic signal and must be considered during thermodynamic calculations based on photoacoustic measurements. The enthalpies of CO substitution by an alkane solvent and subsequent substitution by each Lewis base were determined. Corresponding Mo-L bond energies (kcal mol(-1)) were calculated: L = linear alkanes (13), triethylsilane (26), 1-hexyne (27), 1-hexene (27), and benzene (17). The relative energies are in agreement with computational results. The experimental reaction volume for CO substitution by alkane was positive (15 mL mol(-1)) and negative or close to zero for alkane substitution by a Lewis base (for example, -11 mL mol(-1) for triethylsilane and 3.6 mL mol(-1) for benzene). The errors in the experimental and computational reaction volumes are large and often comparable to the reaction volumes. An improved calibration of the methods as well as a better understanding of the underlying physics involved is needed. For the Lewis bases reported in this study, the second-order rate constants for the displacement of a coordinated alkane are less than diffusion control (5 × 10(6)-4 × 10(7) M(-1) s(-1)) and decrease monotonically with the alkane chain length. The rate constants correlate better with steric effects than with bond energies. An interchange mechanism is consistent with the results.
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