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Title: Monitoring the Formation and Reactivity of Organometallic Alkane and Fluoroalkane Complexes with Silanes and Xe Using Time-Resolved X-ray Absorption Fine Structure Spectroscopy

Journal Article · · Journal of the American Chemical Society
 [1]; ORCiD logo [2];  [3];  [3];  [4];  [5]; ORCiD logo [2];  [2];  [6];  [2];  [7];  [2]; ORCiD logo [8]; ORCiD logo [9]
  1. Rutherford Appleton Lab, Didcot (United Kingdom); The Univ. of Sydney, Sydney (Australia); Univ. of Bath, Bath (United Kingdom)
  2. Univ. of Nottingham, University Park (United Kingdom)
  3. Diamond Light Source, Oxfordshire (United Kingdom)
  4. Rutherford Appleton Lab, Didcot (United Kingdom); Diamond Light Source, Oxfordshire (United Kingdom); Univ. of Southampton, Southampton (United Kingdom)
  5. Diamond Light Source, Oxfordshire (United Kingdom); Univ. of Nottingham, University Park (United Kingdom)
  6. Rutherford Appleton Lab, Didcot (United Kingdom); Univ. of Nottingham, University Park (United Kingdom)
  7. Diamond Light Source, Oxfordshire (United Kingdom); Rutherford Appleton Lab, Oxfordshire (United Kingdom)
  8. Argonne National Lab. (ANL), Lemont, IL (United States)
  9. Rutherford Appleton Lab, Didcot (United Kingdom); Univ. of Nottingham, University Park (United Kingdom); Univ. of Nottingham Ningbo, Ningbo (China)

Complexes with weakly coordinating ligands are often formed in chemical reactions and can play key roles in determining the reactivity, particularly in catalytic reactions. Using time-resolved X-ray absorption fine structure (XAFS) spectroscopy in combination with time-resolved IR (TRIR) spectroscopy and tungsten hexacarbonyl, W(CO)6, we are able to structurally characterize the formation of an organometallic alkane complex, determine the W–C distances, and monitor the reactivity with silane to form an organometallic silane complex. Experiments in perfluorosolvents doped with xenon afford initially the corresponding solvated complex, which is sufficiently reactive in the presence of Xe that we can then observe the coordination of Xe to the metal center, providing a unique insight into the metal–xenon bonding. These results offer a step toward elucidating the structure, bonding, and chemical reactivity of transient species by X-ray absorption spectroscopy, which has sensitivity to small structural changes. The XAFS results indicate that the bond lengths of metal–alkane (W–H–C) bond in W(CO)5(heptane) as 3.07 (±0.06) Å, which is longer than the calculated W–C (2.86 Å) for binding of the primary C–H, but shorter than the calculated W–C (3.12 Å) for the secondary C–H. Here, a statistical average of the calculated W–C alkane bond lengths is 3.02 Å, and comparison of this value indicates that the value derived from the XAFS measurements is averaged over coordination of all C–H bonds consistent with alkane chain walking. Photolysis of W(CO)6 in the presence of HSiBu3 allows the conversion of W(CO)5(heptane) to W(CO)5(HSiBu3) with an estimated W–Si distance of 3.20 (±0.03) Å. Time-resolved TRIR and XAFS experiments following photolysis of W(CO)6 in perfluoromethylcyclohexane (PFMCH) allows the characterization of W(CO)5(PFMCH) with a W–F distance of 2.65 (±0.06) Å, and doping PFMCH with Xe allows the characterization of W(CO)5Xe with a W–Xe bond length of 3.10 (±0.02) Å.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
Engineering and Physical Sciences Research Council (EPSRC); USDOE
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1560858
Journal Information:
Journal of the American Chemical Society, Vol. 141, Issue 29; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 18 works
Citation information provided by
Web of Science

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A Structurally Characterized Cobalt(I) σ‐Alkane Complex journal February 2020
The effect of coordination of alkanes, Xe and CO 21 -OCO) on changes in spin state and reactivity in organometallic chemistry: a combined experimental and theoretical study of the photochemistry of CpMn(CO) 3 journal January 2019
Reversible Encapsulation of Xenon and CH 2 Cl 2 in a Solid‐State Molecular Organometallic Framework (Guest@SMOM) journal November 2019
A Structurally Characterized Cobalt(I) σ‐Alkane Complex journal February 2020

Figures / Tables (12)