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Title: Organometallic complexes of bulky, optically active, C 3-symmetric tris(4 S-isopropyl-5,5-dimethyl-2-oxazolinyl)phenylborate (To P*)

Abstract

A bulky, optically active monoanionic scorpionate ligand, tris(4S-isopropyl-5,5-dimethyl-2-oxazolinyl)phenylborate (To P*), is synthesized from the naturally occurring amino acid l-valine as its lithium salt, Li[To P*] (1). That compound is readily converted to the thallium complex Tl[To P*] (2) and to the acid derivative H[To P*] (3). Group 7 tricarbonyl complexes To P*M(CO) 3 (M = Mn (4), Re (5)) are synthesized by the reaction of MBr(CO) 5 and Li[To P*] and are crystallographically characterized. The ν CO bands in their infrared spectra indicate that π back-donation in the rhenium compounds is greater with To P* than with non-methylated tris(4S-isopropyl-2-oxazolinyl)phenylborate (To P). The reaction of H[To P*] and ZnEt 2 gives To P*ZnEt (6), while To P*ZnCl (7) is synthesized from Li[To P*] and ZnCl 2. The reaction of To P*ZnCl and KOtBu followed by addition of PhSiH 3 provides the zinc hydride complex To P*ZnH (8). In this study, compound 8 is the first example of a crystallographically characterized optically active zinc hydride. We tested its catalytic reactivity in the cross-dehydrocoupling of silanes and alcohols, which provided Si-chiral silanes with moderate enantioselectivity.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1]
  1. Iowa State Univ., Ames, IA (United States)
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1227456
Report Number(s):
IS-J-8725
Journal ID: ISSN 0276-7333
Grant/Contract Number:  
CHE0955635; AC02-07CH11358
Resource Type:
Accepted Manuscript
Journal Name:
Organometallics
Additional Journal Information:
Journal Volume: 34; Journal Issue: 14; Journal ID: ISSN 0276-7333
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Xu, Songchen, Magoon, Yitzhak, Reinig, Regina R., Schmidt, Bradley M., Ellern, Arkady, and Sadow, Aaron D. Organometallic complexes of bulky, optically active, C3-symmetric tris(4S-isopropyl-5,5-dimethyl-2-oxazolinyl)phenylborate (ToP*). United States: N. p., 2015. Web. doi:10.1021/acs.organomet.5b00225.
Xu, Songchen, Magoon, Yitzhak, Reinig, Regina R., Schmidt, Bradley M., Ellern, Arkady, & Sadow, Aaron D. Organometallic complexes of bulky, optically active, C3-symmetric tris(4S-isopropyl-5,5-dimethyl-2-oxazolinyl)phenylborate (ToP*). United States. doi:10.1021/acs.organomet.5b00225.
Xu, Songchen, Magoon, Yitzhak, Reinig, Regina R., Schmidt, Bradley M., Ellern, Arkady, and Sadow, Aaron D. Thu . "Organometallic complexes of bulky, optically active, C3-symmetric tris(4S-isopropyl-5,5-dimethyl-2-oxazolinyl)phenylborate (ToP*)". United States. doi:10.1021/acs.organomet.5b00225. https://www.osti.gov/servlets/purl/1227456.
@article{osti_1227456,
title = {Organometallic complexes of bulky, optically active, C3-symmetric tris(4S-isopropyl-5,5-dimethyl-2-oxazolinyl)phenylborate (ToP*)},
author = {Xu, Songchen and Magoon, Yitzhak and Reinig, Regina R. and Schmidt, Bradley M. and Ellern, Arkady and Sadow, Aaron D.},
abstractNote = {A bulky, optically active monoanionic scorpionate ligand, tris(4S-isopropyl-5,5-dimethyl-2-oxazolinyl)phenylborate (ToP*), is synthesized from the naturally occurring amino acid l-valine as its lithium salt, Li[ToP*] (1). That compound is readily converted to the thallium complex Tl[ToP*] (2) and to the acid derivative H[ToP*] (3). Group 7 tricarbonyl complexes ToP*M(CO)3 (M = Mn (4), Re (5)) are synthesized by the reaction of MBr(CO)5 and Li[ToP*] and are crystallographically characterized. The νCO bands in their infrared spectra indicate that π back-donation in the rhenium compounds is greater with ToP* than with non-methylated tris(4S-isopropyl-2-oxazolinyl)phenylborate (ToP). The reaction of H[ToP*] and ZnEt2 gives ToP*ZnEt (6), while ToP*ZnCl (7) is synthesized from Li[ToP*] and ZnCl2. The reaction of ToP*ZnCl and KOtBu followed by addition of PhSiH3 provides the zinc hydride complex ToP*ZnH (8). In this study, compound 8 is the first example of a crystallographically characterized optically active zinc hydride. We tested its catalytic reactivity in the cross-dehydrocoupling of silanes and alcohols, which provided Si-chiral silanes with moderate enantioselectivity.},
doi = {10.1021/acs.organomet.5b00225},
journal = {Organometallics},
number = 14,
volume = 34,
place = {United States},
year = {2015},
month = {7}
}

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Cited by: 11 works
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Works referencing / citing this record:

CCDC 1419615: Experimental Crystal Structure Determination: JUTHIR : Tricarbonyl-(tris((4S)-isopropyl-5,5-dimethyl-2-oxazolinyl)phenylborate)-manganese
dataset, August 2015

  • Xu, Songchen; Magoon, Yitzhak; Reinig, Regina
  • Cambridge Structural Database (CSD)
  • DOI: 10.5517/cc1jn71g

CCDC 1419616: Experimental Crystal Structure Determination
dataset, January 2015

  • Xu, Songchen; Magoon, Yitzhak; Reinig, Regina R.
  • Cambridge Crystallographic Data Centre, vp
  • DOI: 10.5517/cc1jn72h

CCDC 1419618: Experimental Crystal Structure Determination: JUTJAL : Hydrido-(tris((4S)-isopropyl-5,5-dimethyl-2-oxazolinyl)phenylborate)-zinc
dataset, August 2015

  • Xu, Songchen; Magoon, Yitzhak; Reinig, Regina
  • Cambridge Structural Database (CSD)
  • DOI: 10.5517/cc1jn74k