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Title: C-H bonds are not elongated by coordination to lanthanide metals: Single-crystal neutron diffraction structures of (C{sub 5}Me{sub 5})Y(OC{sub 6}H{sub 3}{sup t}Bu{sub 2})CH(SiMe{sub 3}){sub 2} at 20 K and (C{sub 5}Me{sub 5})La{l{underscore}brace}CH(SiMe{sub 3}){sub 2}{r{underscore}brace} at 15 K

Abstract

The sterically hindered CH(SiMe{sub 3}){sub 2} alkyl group is ubiquitous in organolanthanide chemistry. Although close intramolecular contacts between CH(SiMe{sub 3}){sub 2} and a lanthanide have often been characterized by X-ray diffraction, conclusive evidence as to the exact nature of these interactions (i.e., {alpha}{sub CH}, {alpha}{sub CSi}, {beta}{sub SiC}, and {gamma}{sub CH}) requires accurate determination of all atomic coordinates, including those of the hydrogen atoms. The lack of detailed structural information contrasts sharply with the abundance of transition metal complexes showing well-defined agostic interactions. The authors report the first neutron diffraction studies of such lanthanide complexes on (C{sub 5}Me{sub 5})Y(OAr)CH(SiMe{sub 3}){sub 2} (OAr = O-2,6-C{sub 6}H{sub 3}{sup t}Bu{sub 2}) (1) and (C{sub 5}Me{sub 5})La{r{underscore}brace}CH(SiMe{sub 3}){sub 2}{r{underscore}brace}{sub 2} (2) which clearly show that the {beta}{sub SiC} agostic interaction predominates.

Authors:
; ; ;
Publication Date:
Research Org.:
Brookhaven National Lab., Upton, NY (US)
Sponsoring Org.:
USDOE; Petroleum Research Fund; Netherlands Organization for Scientific Research (NWO)
OSTI Identifier:
20014076
DOE Contract Number:  
AC02-98CH10886
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 121; Journal Issue: 6; Other Information: PBD: 17 Feb 1999; Journal ID: ISSN 0002-7863
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; RARE EARTH COMPOUNDS; BOND LENGTHS; NEUTRON DIFFRACTION; MONOCRYSTALS; ALKYL RADICALS; SILANES; CRYSTAL STRUCTURE

Citation Formats

Klooster, W.T., Brammer, L., Schaverien, C.J., and Budzelaar, P.H.M. C-H bonds are not elongated by coordination to lanthanide metals: Single-crystal neutron diffraction structures of (C{sub 5}Me{sub 5})Y(OC{sub 6}H{sub 3}{sup t}Bu{sub 2})CH(SiMe{sub 3}){sub 2} at 20 K and (C{sub 5}Me{sub 5})La{l{underscore}brace}CH(SiMe{sub 3}){sub 2}{r{underscore}brace} at 15 K. United States: N. p., 1999. Web. doi:10.1021/ja983068b.
Klooster, W.T., Brammer, L., Schaverien, C.J., & Budzelaar, P.H.M. C-H bonds are not elongated by coordination to lanthanide metals: Single-crystal neutron diffraction structures of (C{sub 5}Me{sub 5})Y(OC{sub 6}H{sub 3}{sup t}Bu{sub 2})CH(SiMe{sub 3}){sub 2} at 20 K and (C{sub 5}Me{sub 5})La{l{underscore}brace}CH(SiMe{sub 3}){sub 2}{r{underscore}brace} at 15 K. United States. doi:10.1021/ja983068b.
Klooster, W.T., Brammer, L., Schaverien, C.J., and Budzelaar, P.H.M. Wed . "C-H bonds are not elongated by coordination to lanthanide metals: Single-crystal neutron diffraction structures of (C{sub 5}Me{sub 5})Y(OC{sub 6}H{sub 3}{sup t}Bu{sub 2})CH(SiMe{sub 3}){sub 2} at 20 K and (C{sub 5}Me{sub 5})La{l{underscore}brace}CH(SiMe{sub 3}){sub 2}{r{underscore}brace} at 15 K". United States. doi:10.1021/ja983068b.
@article{osti_20014076,
title = {C-H bonds are not elongated by coordination to lanthanide metals: Single-crystal neutron diffraction structures of (C{sub 5}Me{sub 5})Y(OC{sub 6}H{sub 3}{sup t}Bu{sub 2})CH(SiMe{sub 3}){sub 2} at 20 K and (C{sub 5}Me{sub 5})La{l{underscore}brace}CH(SiMe{sub 3}){sub 2}{r{underscore}brace} at 15 K},
author = {Klooster, W.T. and Brammer, L. and Schaverien, C.J. and Budzelaar, P.H.M.},
abstractNote = {The sterically hindered CH(SiMe{sub 3}){sub 2} alkyl group is ubiquitous in organolanthanide chemistry. Although close intramolecular contacts between CH(SiMe{sub 3}){sub 2} and a lanthanide have often been characterized by X-ray diffraction, conclusive evidence as to the exact nature of these interactions (i.e., {alpha}{sub CH}, {alpha}{sub CSi}, {beta}{sub SiC}, and {gamma}{sub CH}) requires accurate determination of all atomic coordinates, including those of the hydrogen atoms. The lack of detailed structural information contrasts sharply with the abundance of transition metal complexes showing well-defined agostic interactions. The authors report the first neutron diffraction studies of such lanthanide complexes on (C{sub 5}Me{sub 5})Y(OAr)CH(SiMe{sub 3}){sub 2} (OAr = O-2,6-C{sub 6}H{sub 3}{sup t}Bu{sub 2}) (1) and (C{sub 5}Me{sub 5})La{r{underscore}brace}CH(SiMe{sub 3}){sub 2}{r{underscore}brace}{sub 2} (2) which clearly show that the {beta}{sub SiC} agostic interaction predominates.},
doi = {10.1021/ja983068b},
journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 6,
volume = 121,
place = {United States},
year = {1999},
month = {2}
}