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Dinuclear Chlorido‐, Alkyl(chlorido)‐, and Hydridoyttrium Complexes Supported by μ‐Bridging‐Silyl‐Linked Bis(amidinate) Ligands

Title: Dinuclear Chlorido‐, Alkyl(chlorido)‐, and Hydridoyttrium Complexes Supported by μ‐Bridging‐Silyl‐Linked Bis(amidinate) Ligands
Authors: Skvortsov, Grigorii G.; Tolpyguin, Alexei O.; Fukin, Georgy K.; Cherkasov, Anton V.; Trifonov, Alexander A.
Source: European Journal of Inorganic Chemistry ; volume 2010, issue 11, page 1655-1662 ; ISSN 1434-1948 1099-0682
Publisher Information: Wiley
Publication Year: 2010
Collection: Wiley Online Library (Open Access Articles via Crossref)
Description: A chloridoyttrium complex supported by a silyl‐linked bis(amidinate) ligand, [(Me 2 Si{NC(Ph)N(2,6‐ i Pr 2 –C 6 H 3 )} 2 ) 2 (YCl) 2 (μ‐Cl)] – [Li(thf) 4 ] + ( 2 ) (thf = tetrahydrofuran), was synthesized by the reaction of equimolar amounts of anhydrous YCl 3 and lithium amidinate [(Me 2 Si{NC(Ph)N(2,6‐ i Pr 2 –C 6 H 3 )} 2 ) 2 Li 3 ] – [Li(thf) 4 ] + ( 1 ) in thf at 20 °C. Complex 2 was isolated after recrystallization from a thf/hexane mixture in 72 % yield. Single‐crystal X‐ray structure analysis has revealed that 2 is a dinuclear compound composed of a discrete complex anion [(Me 2 Si{NC(Ph)N(2,6‐ i Pr 2 –C 6 H 3 )} 2 ) 2 (YCl) 2 (μ‐Cl)] – , containing one μ‐bridging and two terminal chloride ligands, and a cation [Li(thf) 4 ] + . The formation of a dimeric structure results from the coordination of amidinate fragments of the same dianionic ligand on two different yttrium ions and the presence of a μ‐bridging chloride ligand. Alkylation of 2 with one equivalent of Me 3 SiCH 2 Li in toluene afforded an alkyl(chlorido)yttrium complex, [Me 2 Si{NC(Ph)N(2,6‐ i Pr 2 –C 6 H 3 )} 2 ] 2 [Y(thf)](μ‐Cl)[Y(CH 2 SiMe 3 )] ( 3 ). X‐ray crystal structure investigation has shown that 3 is a dimeric complex as a result of the “spanning” coordination mode of the ansa ‐bis(amidinate) ligands and the presence of one μ 2 ‐chloride ligand, while the alkyl group remains terminal. Treatment of the in situ generated alkyl derivative [Me 2 Si{NC(Ph)N(2,6‐ i Pr 2 –C 6 H 3 )} 2 ] 2 [Y(CH 2 SiMe 3 )] 2 ( 4 ) with PhSiH 3 in toluene results in the formation of the corresponding hydridoyttrium complex [Me 2 Si{NC(Ph)N(2,6‐ i Pr 2 –C 6 H 3 )} 2 Y(μ‐H)] 2 ( 5 ), which was isolated after recrystallization from toluene in 73 % yield. According to the X‐ray crystal structure analysis, 5 adopts a dimeric structure with two μ‐bridging bis(amidinate) and two μ 2 ‐hydrido ligands.
Document Type: article in journal/newspaper
Language: English
DOI: 10.1002/ejic.200901161
Availability: https://doi.org/10.1002/ejic.200901161; https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fejic.200901161; https://onlinelibrary.wiley.com/doi/pdf/10.1002/ejic.200901161; https://onlinelibrary.wiley.com/doi/full-xml/10.1002/ejic.200901161
Rights: http://onlinelibrary.wiley.com/termsAndConditions#vor
Accession Number: edsbas.306A134D
Database: BASE