Metallocene Allyl Reactivity in the Presence of Alkenes Tethered to Cyclopentadienyl Ligands

Evans, William J.; Kozimor, Stosh A.; Brady, Jason C.; Davis, Benjamin L.; Nyce, Gregory W.; Seibel, Christopher A.; Ziller, Joseph W.; Doedens, Robert J.

doi:10.1021/om049286x

Cited by 58 publications

(111 citation statements)

References 54 publications

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“…1, 2010 227 0.05-0.12 Å . This difference in metal to atom bond distances is common for f element allyl complexes 22 and has been observed previously in uranium amidinate complexes. 23 In all cases, the U-N(hpp) distances adjacent to the anionic X ligands are shorter than those further from X.…”

Section: Articlesupporting

confidence: 79%

Uranium Metallocene Complexes of the 1,3,4,6,7,8-Hexahydro-2H-pyrimido[1,2-a]pyrimidinato Ligand, (hpp)⁻

et al. 2009

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The utility of the 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinato ligand, (hpp)(-), in uranium chemistry has been probed by synthesizing metallocene complexes and studying their reactivity. (C(5)Me(5))(2)UMe(2) reacts with 1 equiv of Hhpp to form (C(5)Me(5))(2)(hpp)UMe, 1, which does not react further with Hhpp. (C(5)Me(5))(2)UCl(2) reacts with Khpp to form (C(5)Me(5))(2)(hpp)UCl, 2, which similarly does not react with additional Khpp. Complex 2 reacts with NaN(3) to form the azide complex, (C(5)Me(5))(2)(hpp)UN(3), 3. The trivalent uranium (hpp)(-) metallocene complex, (C(5)Me(5))(2)(hpp)U, 4, can be synthesized by the reaction of [(C(5)Me(5))(2)U][BPh(4)] with Khpp and from 2 with KC(8). Complex 4 can be oxidized with Ph(3)P horizontal lineSe to produce the tetravalent product, [(C(5)Me(5))(2)(hpp)U](2)(mu-Se), 5. The reaction of 4 with Me(3)SiN(3) provides the pentavalent uranium complex, (C(5)Me(5))(2)(hpp)U(=NSiMe(3)), 6.

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Section: Articlesupporting

confidence: 79%

Uranium Metallocene Complexes of the 1,3,4,6,7,8-Hexahydro-2H-pyrimido[1,2-a]pyrimidinato Ligand, (hpp)⁻

et al. 2009

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“…These complexes had been previously synthesized and characterized [13]. In particular, the 1 H NMR analysis established non-fluxional allyl group with 1H/2H/2H allyl signals.…”

Section: Allyl Complexes For the Polymerization Of Isoprenementioning

confidence: 99%

“…Thereafter, allylic-substituted rare earths, ranging from mono-to tetra-substituted allyl complexes, have been explored, and the group of Taube was probably the most successful in this area during the 1980s and 1990s [8]. In terms of reactivity, the allyl moiety is of specific interest because it makes it possible to carry out a certain number of elementary organometallic reactions, such as those involved in catalytic processes (insertion reactions [9], hydrogenolysis [10,11], hydrosilylation [12], alkyl exchange [13], etc.). Consequentially, the [RE-(allyl)] species has demonstrated its ability to catalyze polymerization reactions, with a particular behavior towards non-polar monomers (Scheme 1), some of which are highly stereo-selective [14][15][16].…”

Section: Introductionmentioning

confidence: 99%

Recent Advances in Rare Earth Complexes Bearing Allyl Ligands and Their Reactivity towards Conjugated Dienes and Styrene Polymerization

et al. 2017

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“…A concentrated hexane mixture at 243 K yielded dark orange crystals of 7 (104 mg, 97%). 1 H NMR (C 6 D 6 , 298 K): δ 8.7 (s, C 5 Me 5 , 30H), −0.6 (d, 9 Hz, CH 2 CHCH 2 , 1H), −2.8 (d, 16 Hz, CH 2 CH CH 2 , 1H), ( (8). A brown-red solution of 2 (100 mg, 0.168 mmol) in toluene (15 mL) was degassed via three freeze−pump−thaw cycles.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Synthesis and CO₂ Insertion Reactivity of Allyluranium Metallocene Complexes

Webster

Evans

2012

Organometallics

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The U 4+ metallocene allyl chloride complexes (C 5 Me 5 ) 2 U[η 3 -CH 2 C(R)CH 2 ]Cl (R = H, Me) can be synthesized by reaction of (C 5 Me 5 ) 2 UCl 2 with 1 equiv of the corresponding allyl Grignard reagents, [CH 2 C(R)CH 2 ]MgCl, in hydrocarbon solvents. Bis(allyl)uranium complexes can also be obtained in this manner using 2 equiv of the corresponding allyl Grignard, and X-ray crystallographic studies reveal the presence of both η 3 -and η 1

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Metallocene Allyl Reactivity in the Presence of Alkenes Tethered to Cyclopentadienyl Ligands

Cited by 58 publications

References 54 publications

Uranium Metallocene Complexes of the 1,3,4,6,7,8-Hexahydro-2H-pyrimido[1,2-a]pyrimidinato Ligand, (hpp)⁻

Uranium Metallocene Complexes of the 1,3,4,6,7,8-Hexahydro-2H-pyrimido[1,2-a]pyrimidinato Ligand, (hpp)⁻

Recent Advances in Rare Earth Complexes Bearing Allyl Ligands and Their Reactivity towards Conjugated Dienes and Styrene Polymerization

Synthesis and CO₂ Insertion Reactivity of Allyluranium Metallocene Complexes

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Metallocene Allyl Reactivity in the Presence of Alkenes Tethered to Cyclopentadienyl Ligands

Cited by 58 publications

References 54 publications

Uranium Metallocene Complexes of the 1,3,4,6,7,8-Hexahydro-2H-pyrimido[1,2-a]pyrimidinato Ligand, (hpp)−

Uranium Metallocene Complexes of the 1,3,4,6,7,8-Hexahydro-2H-pyrimido[1,2-a]pyrimidinato Ligand, (hpp)−

Recent Advances in Rare Earth Complexes Bearing Allyl Ligands and Their Reactivity towards Conjugated Dienes and Styrene Polymerization

Synthesis and CO2 Insertion Reactivity of Allyluranium Metallocene Complexes

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Uranium Metallocene Complexes of the 1,3,4,6,7,8-Hexahydro-2H-pyrimido[1,2-a]pyrimidinato Ligand, (hpp)⁻

Uranium Metallocene Complexes of the 1,3,4,6,7,8-Hexahydro-2H-pyrimido[1,2-a]pyrimidinato Ligand, (hpp)⁻

Synthesis and CO₂ Insertion Reactivity of Allyluranium Metallocene Complexes