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On the kinetics and mechanism of the conversion of Cr(CO)5(κ1-P-dppm) to Cr(CO)4(κ2-P,P′-dppm) (dppm = 1,2-diphenylphosphinomethane): an alternative hypothesis

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Abstract

The data from a previously reported kinetic evaluation dealing with the conversion of Cr(CO)5(κ1-P-dppm) (1: dppm = 1,2-diphenylphosphinomethane) into the corresponding chelated complex Cr(CO)4(κ2-P,P′-dppm) (2), via CO loss, is re-evaluated. The conclusion is that the process is more likely to involve a rate-determining step that is first-order in [Cr(CO)5(κ1-P-dppm)], as opposed to the previously reported zero-order model as proposed. This implies CO loss from 1, by presumably either an I d or more likely a Dissociative (D: S N 1-type) mechanism, leads to 2. This hypothesis is compared and contrasted to reported data and comparisons are made to similar processes involving related Group VI metal carbonyl species.

Graphical Abstract

\( \mathop {{\text{Cr}}\left( {\text{CO}} \right)_{5} (\upkappa^{1} -P-dppm) + \Delta }\limits_{{\mathbf{1}}} \to \mathop {{\text{Cr}}\left( {\text{CO}} \right)_{4} (\upkappa^{2} -P,P^{{\prime }} {\text{-dppm}}) + {\text{CO}}}\limits_{{\mathbf{2}}} \)

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Notes

  1. An electronic version of the manuscript referred to in Ref. [32] is available at http://journals.tubitak.gov.tr/chem/abstract.htm?id=164.

  2. It should be noted that to firmly establish zero- versus first-order kinetics that data points covering at least two half-lives are typically required. The data reported [32] is lacking in this regard at both 373 and 378 K temperatures. However, the 383 K data set does cover (barely) two half-lives for calculated first-order decay (t ½ = 5.8 h; t ∞ = 12.1 h). It is intuitively unlikely that kinetic order would be variable over a single concentration of 1 and under the narrow temperature range studied [32]. Hence, our conclusions presented herein rely on the higher temperature data being representative of the half-life profile in the complete 373–383 K temperature range.

  3. In first-order processes, the expression ln(k y/k x) = E a ([1/T x ] − [1/T y ])R −1 can be used to determine E a [5, 6, 9]. We employed this equation using all three derived k values to estimate the error of our calculated E a value. In addition, the activity parameter A was found to be 1.2 (± 0.2) × 1020 via the expression ln(k) = ln(A) – E a/RT.

  4. The aim herein has been to present a plausible alternative mechanistic hypothesis, fully in-line with literature precedent [40] and the established concepts of metal carbonyl ligand substitution, that a first-order model is very likely operating during the conversion of 1 into 2. The seminal 1973 study by Connor, differing only in the solvent employed, strongly supports our view.

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Acknowledgements

This work was supported by Ryerson University. The author is indebted to Professor Daniel A. Foucher, Professor R. Stephen Wylie (both of Ryerson University) and Professor Emeritus John M. Roscoe (Acadia University) for a number of fruitful discussions with respect to various aspects of this manuscript.

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  1. Department of Chemistry and Biology, Ryerson University, 350 Victoria Street, Toronto, ON, M5B 2K3, Canada

    Robert A. Gossage

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Correspondence to Robert A. Gossage.

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Gossage, R.A. On the kinetics and mechanism of the conversion of Cr(CO)5(κ1-P-dppm) to Cr(CO)4(κ2-P,P′-dppm) (dppm = 1,2-diphenylphosphinomethane): an alternative hypothesis. Transit Met Chem 43, 39–43 (2018). https://doi.org/10.1007/s11243-017-0191-3

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