“…The most noticeable resonances in the 13 C{ 1 H} NMR spectrum are those due to the side chain, which are observed at 71.2 (CH 2 O), 58.6 (CH 3 ), and 28.3 ppm (CH 2 ) ( 3 ) and at 70.0 (CH 2 O), 58.5 (CH 3 ), and 27.3 ppm (CH 2 ) ( 4 ). These data are consistent with the noncoordination of the pendant ether to the iridium atom. ,5c,f, …”
Section: Resultssupporting
confidence: 77%
“…In this context it should be noted that the derivative Ir{η 5 -Cp N }(COE) 2 (Cp N = C 5 H 4 (CH 2 ) 2 N(CH 3 ) 2 ), containing NMe 2 instead of OMe as a pendant donor group, reacts with I 2 to give the mononuclear species IrI 2 {η 5 ( C 5 ),κ N -Cp N }, which contains the pendant amino group coordinated to the iridium atom 5a. A similar finding has been reported for the related half-sandwich rhodium complexes [Rh(η 5 -Cp O )I(μ-I)] 2 and RhCl 2 {η 5 ( C 5 ),κ N -Cp N } . This behavior agrees well with the greater coordination ability of the amine compared with that of the ether group, which has been also observed for the titanium complexes TiCl n R 3 - n (Cp E ) (Cp E = Cp N , Cp O ; n = 0−3; R = Me). 5e,f 1 Molecular diagram of complex 4 .…”
Treatment of [Ir(µ-Cl)(COE) 2 ] 2 (1) with LiCp O gives Ir(η 5 -Cp O )(COE) 2 (2; Cp O ) C 5 H 4 (CH 2 ) 2 OCH 3 , COE ) cis-cyclooctene), which reacts with X 2 to afford the iridium(III) derivatives [Ir(η 5 -Cp O )X(µ-X)] 2 (X ) I (3), Cl (4)). Complexes 3 and 4 react with P i Pr 3 to yield the corresponding species Ir(η 5 -Cp O )(P i -Pr 3 )X 2 (X ) I ( 5), Cl ( 6)), which by addition of LiHBEt 3 give Ir(η 5 -Cp O )(P i Pr 3 )H 2 (7). The reactions of 5 and 6 with 2.0 equiv of AgBF 4 in acetonitrile lead to [Ir(η 5 -Cp O )(P i Pr 3 )(NCMe) 2 ][BF 4 ] 2 (8). Treatment of 3 with 2.0 equiv of HSiEt 3 per iridium affords the monohydride dimer [Ir(η 5 -Cp O )I] 2 (µ-H)(µ-I) (9). Complex 4 reacts with 4.0 equiv of HSiEt 3 per iridium to give the iridium(V) silyl trihydride derivative IrH 3 (η 5 -Cp O )(SiEt 3 ) (10), which in the presence of excess of HSiEt 3 is transformed into IrH 2 (η 5 -Cp O )-(SiEt 3 ) 2 (11). Treatment at -40 °C of 4 with 2.0 equiv of HSiEt 3 per iridium leads to a mixture of the hydride dichloro triethylsilyl complex IrH(η 5 -Cp O )Cl 2 (SiEt 3 ) (12), the dihydride chloro triethylsilyl compound IrH 2 (η 5 -Cp O )Cl(SiEt 3 ) (14), and the monohydride dimer [Ir(η 5 -Cp O )Cl] 2 (µ-H)(µ-Cl) (16). Complex 16 has been also prepared by reaction of 4 with 1.0 equiv of HSiEt 3 per iridium. Complex 10 is easily deuterated in C 6 D 6 at 80 °C. The X-ray structures of 4, 8, and 9 are also reported.
“…The most noticeable resonances in the 13 C{ 1 H} NMR spectrum are those due to the side chain, which are observed at 71.2 (CH 2 O), 58.6 (CH 3 ), and 28.3 ppm (CH 2 ) ( 3 ) and at 70.0 (CH 2 O), 58.5 (CH 3 ), and 27.3 ppm (CH 2 ) ( 4 ). These data are consistent with the noncoordination of the pendant ether to the iridium atom. ,5c,f, …”
Section: Resultssupporting
confidence: 77%
“…In this context it should be noted that the derivative Ir{η 5 -Cp N }(COE) 2 (Cp N = C 5 H 4 (CH 2 ) 2 N(CH 3 ) 2 ), containing NMe 2 instead of OMe as a pendant donor group, reacts with I 2 to give the mononuclear species IrI 2 {η 5 ( C 5 ),κ N -Cp N }, which contains the pendant amino group coordinated to the iridium atom 5a. A similar finding has been reported for the related half-sandwich rhodium complexes [Rh(η 5 -Cp O )I(μ-I)] 2 and RhCl 2 {η 5 ( C 5 ),κ N -Cp N } . This behavior agrees well with the greater coordination ability of the amine compared with that of the ether group, which has been also observed for the titanium complexes TiCl n R 3 - n (Cp E ) (Cp E = Cp N , Cp O ; n = 0−3; R = Me). 5e,f 1 Molecular diagram of complex 4 .…”
Treatment of [Ir(µ-Cl)(COE) 2 ] 2 (1) with LiCp O gives Ir(η 5 -Cp O )(COE) 2 (2; Cp O ) C 5 H 4 (CH 2 ) 2 OCH 3 , COE ) cis-cyclooctene), which reacts with X 2 to afford the iridium(III) derivatives [Ir(η 5 -Cp O )X(µ-X)] 2 (X ) I (3), Cl (4)). Complexes 3 and 4 react with P i Pr 3 to yield the corresponding species Ir(η 5 -Cp O )(P i -Pr 3 )X 2 (X ) I ( 5), Cl ( 6)), which by addition of LiHBEt 3 give Ir(η 5 -Cp O )(P i Pr 3 )H 2 (7). The reactions of 5 and 6 with 2.0 equiv of AgBF 4 in acetonitrile lead to [Ir(η 5 -Cp O )(P i Pr 3 )(NCMe) 2 ][BF 4 ] 2 (8). Treatment of 3 with 2.0 equiv of HSiEt 3 per iridium affords the monohydride dimer [Ir(η 5 -Cp O )I] 2 (µ-H)(µ-I) (9). Complex 4 reacts with 4.0 equiv of HSiEt 3 per iridium to give the iridium(V) silyl trihydride derivative IrH 3 (η 5 -Cp O )(SiEt 3 ) (10), which in the presence of excess of HSiEt 3 is transformed into IrH 2 (η 5 -Cp O )-(SiEt 3 ) 2 (11). Treatment at -40 °C of 4 with 2.0 equiv of HSiEt 3 per iridium leads to a mixture of the hydride dichloro triethylsilyl complex IrH(η 5 -Cp O )Cl 2 (SiEt 3 ) (12), the dihydride chloro triethylsilyl compound IrH 2 (η 5 -Cp O )Cl(SiEt 3 ) (14), and the monohydride dimer [Ir(η 5 -Cp O )Cl] 2 (µ-H)(µ-Cl) (16). Complex 16 has been also prepared by reaction of 4 with 1.0 equiv of HSiEt 3 per iridium. Complex 10 is easily deuterated in C 6 D 6 at 80 °C. The X-ray structures of 4, 8, and 9 are also reported.
“…Pt complex with structurally similar trithiacyclononane ligand (11b) also promotes ethylene polymerization in the presence of MAO [203]. Recently, Rh complex (11c) with high activity was reported by Jin [204]. He also reported complexes of the metal centers that are not common in olefin polymerization catalysts, such as Ag (11d) [205] and Ir (11e) [206].…”
Section: Polymerization Of Olefins By Other Late Transition Metal Catmentioning
Diimine Pd and Ni complexes catalyze the polymerization of ethylene, propylene, and a-olefins. The reaction involves isomerization of the growing terminal (chain walking) and, as its result, produces highly branched polyethylene and poy(a-olefin)s having a smaller number of the alkyl substituents than expected from the monomer structure. Ni complexes with salicylaldimine or iminocarboxamide ligands and Pd complexes with phosphinesulfonate ligands are used as single component catalysts for ethylene polymerization. Especially, the latter catalysts show tolerance towards polar functional groups and promote copolymerization of ethylene with wide varieties of polar monomers. The Pd and Ni complexes are able to catalyze ethylene polymerization in aqueous media to yield polyethylene particles. Fe and Co complexes with bis(imino)pyridine ligands show high catalytic activity for ethylene polymerization to yield linear polyethylene. Complexes of the metals such as Rh, Ir, Ru, and Ag were revealed to become catalytically active by proper design of the ligand. Not only monometallic complexes but also bimetallic or multimetallic complexes are used for ethylene polymerization. Late transition metal complexes catalyze selective cyclopolymerization of non-conjugated dienes and trienes to afford the polymers with cycloalkane groups with controlled stereochemistry.
“…Our previous work indicated that O-and S-functionalized rhodium complexes showed high activities for ethylene polymerization [7]. In this study, we introduce two different functional ligands to cobalt complexes and make further investigations into the effects of the donor ligands and O-and S-functionalized substituents on cyclopentadienyl as a weak coordination system.…”
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
