St. Clair, Martin and Schaefer, William P. and Bercaw, John E. (1991) Reactivity of permethylscandocene derivatives with acetylene. Structure of acetylenediylbis(permethylscandocene), (η^5-C_5Me_5)_2Sc-C≡C-Sc(η^5-C_5Me_5)_2. Organometallics, 10 (3). pp. 525-527. ISSN 0276-7333. doi:10.1021/om00049a001. https://resolver.caltech.edu/CaltechAUTHORS:20180521-105844972
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Abstract
Excess acetylene reacts with Cp*_2Sc-R (Cp* = η-C5Me_5; R = H, alkyl, aryl, alkenyl, alkynyl, amide) below -78 °C to yield R-H and Cp*_2Sc-C≡CH; the latter then reacts with excess C_2H_2 to form polyacetylene. Cp*_2Sc-C≡CH cleanly decomposes to Cp*_2Sc-C≡C-ScCp*_2, most likely via u bond metathesis involving the Sc-acetylide and terminal C-H bonds for two molecules of Cp*_2Sc-C≡CH. The structure of this unusual acetylenediyl-bridged dimer has been determined by X-ray diffraction methods. It crystallizes with a half-molecule of toluene per scandium dimer in the tetragonal system, space group P42_1c (No. 114), with a = 15.057 (3) Å, c = 18.617 (6) Å, V = 4220.7 (18) Å^3, and z = 4.
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| Alternate Title: | Reactivity of permethylscandocene derivatives with acetylene. Structure of acetylenediylbis(permethylscandocene), (.eta.5-C5Me5)2ScC.tplbond.CSc(.eta.5-C5Me5)2 | |||||||||
| Additional Information: | © 1991 American Chemical Society. Received June 27, 1990. This work was supported by the USDOE Office of Energy Research, Office of Basic Energy Science (Grant No. DE-FG03-85ER13431), and by Shell Companies Foundation, which are gratefully acknowledged. We thank the NSF (Grant No. CHE-8219039) for funds to purchase the X-ray diffractometer. | |||||||||
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| Issue or Number: | 3 | |||||||||
| DOI: | 10.1021/om00049a001 | |||||||||
| Record Number: | CaltechAUTHORS:20180521-105844972 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20180521-105844972 | |||||||||
| Official Citation: | Reactivity of permethylscandocene derivatives with acetylene. Structure of acetylenediylbis(permethylscandocene), (.eta.5-C5Me5)2ScC.tplbond.CSc(.eta.5-C5Me5)2 Martin. St. Clair, William P. Schaefer, and John E. Bercaw Organometallics 1991 10 (3), 525-527 DOI: 10.1021/om00049a001 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 86498 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | George Porter | |||||||||
| Deposited On: | 21 May 2018 18:17 | |||||||||
| Last Modified: | 15 Nov 2021 20:39 |
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