2010
DOI: 10.1002/ejic.201000330
|View full text |Cite
|
Sign up to set email alerts
|

Lanthanide Complexes Coordinated by a Dianionic Bis(amidinate) Ligand with a Rigid Naphthalene Linker

Abstract: The synthetic pathway to a new bis(amidine) ligand with a conformationally rigid naphthalene linker, 1,8‐C10H6[NHC(tBu)=N(2,6‐Me2–C6H3)][N=C(tBu)NH(2,6‐Me2–C6H3)] (3) was elaborated. Deprotonation of this bis(amidine) ligand with two equivalents of nBuLi and subsequent reaction with anhydrous LnCl3 (Ln = Y, Nd, Sm) allowed the synthesisof the chlorido complexes [1,8‐C10H6{NC(tBu)N‐2,6‐Me2–C6H3}2]YCl(dme) (4), [1,8‐C10H6{NC(tBu)N‐2,6‐Me2–C6H3}2]Nd(dme)(μ‐Cl)2Li(dme) (5), and [1,8‐C10H6{NC(tBu)N‐2,6‐Me2–C6H3}2]S… Show more

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...
2
1
1
1

Citation Types

8
35
1

Year Published

2013
2013
2019
2019

Publication Types

Select...
8

Relationship

4
4

Authors

Journals

citations
Cited by 45 publications
(44 citation statements)
references
References 46 publications
8
35
1
Order By: Relevance
“…Another popular method for the synthesis of organolanthanide complexes is the metathetical reaction. For example, several amidinate lanthanide chlorides [Me 3 SiNC(Ph)N(CH 2 ) 3 NC(Ph)NSiMe 3 ] Ln Cl(THF) 2 ( Ln = Y, Yb),8a,8b [(Me 2 Si{NC(Ph)N(2, 6‐ i Pr 2 –C 6 H 3 )} 2 ) 2 (YCl) 2 (μ‐Cl)] – [Li(THF) 4 ] + ,8c [1, 8‐C 10 H 6 {NC( t Bu)N‐2, 6‐Me 2 –C 6 H 3 } 2 ]YCl(DME),8d and [C 6 H 4 ‐1, 2‐{NC( t Bu)N(2, 6‐ R 2 C 6 H 3 )} 2 ]Y(THF)(μ‐Cl) 2 Li(THF) 2 ( R = Me, i Pr)8e were reported to be synthesized by the reaction of lanthanide chloride with lithium salts of corresponding linked bis(amidinate) dianionic ligands. Therefore, the new linked bis(β‐ketoiminato) ytterbium chloride and its derivatives were conveniently synthesized by this method in the presented work.…”
Section: Resultssupporting
confidence: 82%
“…Another popular method for the synthesis of organolanthanide complexes is the metathetical reaction. For example, several amidinate lanthanide chlorides [Me 3 SiNC(Ph)N(CH 2 ) 3 NC(Ph)NSiMe 3 ] Ln Cl(THF) 2 ( Ln = Y, Yb),8a,8b [(Me 2 Si{NC(Ph)N(2, 6‐ i Pr 2 –C 6 H 3 )} 2 ) 2 (YCl) 2 (μ‐Cl)] – [Li(THF) 4 ] + ,8c [1, 8‐C 10 H 6 {NC( t Bu)N‐2, 6‐Me 2 –C 6 H 3 } 2 ]YCl(DME),8d and [C 6 H 4 ‐1, 2‐{NC( t Bu)N(2, 6‐ R 2 C 6 H 3 )} 2 ]Y(THF)(μ‐Cl) 2 Li(THF) 2 ( R = Me, i Pr)8e were reported to be synthesized by the reaction of lanthanide chloride with lithium salts of corresponding linked bis(amidinate) dianionic ligands. Therefore, the new linked bis(β‐ketoiminato) ytterbium chloride and its derivatives were conveniently synthesized by this method in the presented work.…”
Section: Resultssupporting
confidence: 82%
“…The lengths of the covalent Ln(1)–N(5) bond ( 3 : 2.295(3) Å; 4 : 2.389(3)–2.408(4) Å) are comparable with those in the formerly described amido yttrium [{Me 3 SiNC(Ph)N} 2 (CH 2 ) 3 ]Y(2,6‐Pr i 2 C 6 H 3 NH)DME (2.237(4) Å), {(3,5‐Me 2 C 3 HN 2 ) 3 B}Y[κ 3 ‐(4‐NH=(C 8 N 2 H 4 )(2‐NHC 6 H 4 ))]{(Me 2 N) 3 P=O} (2.309(5) Å) and neodymium complexes [3,5‐Bu t 2 ‐2‐O‐C 6 H 2 CH=N‐C 5 H 4 N] 2 NdN(SiMe 3 ) 2 (2.385(3) Å), [{Me 3 SiNC(Ph)N} 2 (CH 2 ) 3 ]Nd(2,6‐Pr i 2 C 6 H 3 NH)DME (2.342(7) Å), [{(NC 5 H 4 )NHCH 2 (3,5‐Bu t 2 ‐C 6 H 2 ‐2‐OH)}NdN(SiMe 3 ) 2 (THF)] 2 (2.372(3) Å) . The Ln–N amidinate distances in 3 and 4 are somewhat different (κ 4 ‐NNOO‐ligand 2.378(3)–2.379(3) Å ( 3 ), 2.473(2)–2.483(2) Å ( 4 ); κ 2 ‐NN‐ligand 2.21(2)–2.45(2) Å, average 2.34(6) Å ( 3 ), 2.415(5)–2.487(4) Å, average 2.46(2) Å ( 4 )), but are comparable with the corresponding values measured in the related seven‐coordinate yttrium amidinate complexes [{1,3‐C 6 H 4 (NC(Ph)NSiMe 3 ) 2 } 3 Y(THF)Y(µ‐Cl)Li(THF) 3 ] (2.341(6), 2.455(6) Å), [Y{ o ‐CH 3 O‐C 6 H 4 NC(Ph)N(SiMe 3 )}Cl 2 (THF) 2 ] 2 (2.384(2), 2.375(2) Å), [(2,6‐Et 2 C 6 H 3 N) 2 C(4‐Me‐C 6 H 4 )] 2 Y(THF)(Cl)(µ‐Cl)Li(THF) 3 (2.402(6)–2.464(5) Å), [1,8‐C 10 H 6 {NC(Bu t )N‐2,6‐Me 2 ‐C 6 H 3 } 2 ]YCl(DME) (2.331(1)–2.369(1) Å) [{Me 3 SiNC(Ph)N} 2 (CH 2 ) 3 ]YCl(DME) (2.360(3)–2.379(3) Å) and seven‐coordinate neodymium complexes (2.385(2)–2.604(7) Å) , . The C–N bond lengths within the amidinate fragments in 3 and 4 fall into a narrow interval ( 3 : 1.321(8)–1.333(9) Å, 4 : 1.313(4)–1.333(9) Å) thus being indicative of delocalization of the negative charge over the NCN fragments.…”
Section: Resultssupporting
confidence: 66%
“…5) but is somewhat longer than the corresponding bond lengths in other known heptacoordinated bis(amidinate) yttrium complexes (([C 3 H 6 {NC(Ph)NSiMe 3 } 2 ]YCl(DME) (2.369(3) Å) 8 and C 10 H 6 {NC(Bu t )N 2,6 Me 2 C 6 H 3 } 2 YCl(DME) (2.350(1) Å). 9 It should be mentioned that the distances to the "internal" nitrogen atoms of the amidinate frag ments Y(1)-N(1) and Y(1)-N(2) (2.315(2), 2.336(1) Å) are noticeably shorter compared to the distances to the "external" Y(1)-N(3) and Y(1)-N(4) moieties (2.478(2), 2.435(1) Å). A similar tendency was observed previously for related compounds.…”
Section: Methodsmentioning
confidence: 99%