Tetrahydroborate complexes of uranium: Preparation and crystal structure of mixed-valent [Na(THF)6] [(C5Me5)U(BH4)3]2

Ryan, R. R.; Salazar, Kenneth V.; Sauer, Nancy N.; Ritchey, John M.

doi:10.1016/s0020-1693(00)83151-5

Cited by 18 publications

(14 citation statements)

References 20 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Synthesis and Reactivity. The reaction of anhydrous ThCl 4 with 1 equiv of Cp*MgCl·THF has previously been reported to produce the mono(pentamethylcyclopentadienyl) species Cp*ThCl 3 (THF) 2 ·THF (eq 1) 4a…”

Section: Resultsmentioning

confidence: 99%

“…In the case of thorium, the range of mono(pentamethylcyclopentadienyl) complexes described in the literature is extremely limited. Marks and co-workers have reported the preparation of the trichloride derivative Cp*ThCl 3 (THF) 2 ·THF (eq 1) and the subsequent reaction of this complex with 3 equiv of benzyllithium to form the tris(benzyl) complex Cp*Th(CH 2 C 6 H 5 ) 3 (eq 2) 4a. More recently, Sattelberger et al .…”

Section: Introductionmentioning

confidence: 99%

“…More recently, Sattelberger et al . have described the isolation of the mixed-ring complex (η-C 8 H 8 )(η-C 5 Me 5 )ThCl(THF) x from the reaction of (η-C 8 H 8 )ThCl 2 (THF) 2 with a pentamethylcyclopentadienyl Grignard reagent and its subsequent derivatization to produce (η-C 8 H 8 )(η-C 5 Me 5 )Th[CH(SiMe 3 ) 2 ], [(η-C 8 H 8 )(η-C 5 Me 5 )ThH] x , and (η-C 8 H 8 )(η-C 5 Me 5 )Th(μ-Cl) 2 Mg(CH 2 - t -Bu)(THF) 4b…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Mono(pentamethylcyclopentadienyl)thorium Chemistry: Synthesis, Structural Characterization, and Reactivity of Aryloxide and Alkyl Derivatives

et al. 1996

View full text Add to dashboard Cite

Reaction of ThBr4(THF)4 with 1 equiv of Cp*MgBr(THF) (Cp* = η-C5Me5) produces the mono(pentamethylcyclopentadienyl) complex Cp*ThBr3(THF)3 (1). Treatment of 1 with 1 or 2 equiv of KOAr (Ar = 2,6-t-Bu2C6H3) yields the mono- and bis(aryloxide) species Cp*ThBr2(OAr)(THF) (2) and Cp*ThBr(OAr)2 (3), respectively. Alkylation of 2 with 2 equiv of Me3SiCH2MgCl leads to isolation of the bis(alkyl) complex Cp*Th(OAr)(CH2SiMe3)2 (4), while 3 reacts with 1 equiv of MeMgBr to form the mono(alkyl) derivative Cp*ThMe(OAr)2 (5). 4 reacts with dihydrogen to produce the trimeric thorium dihydride [Cp*ThH2(OAr)]3 (6), while thermolysis of 4 in the presence of triphenylphosphine oxide leads to the isolation of the metallacyclic species Cp*Th(OC6H3-t-BuCMe2CH2)(OAr)(OPPh3) (7). In the presence of 1 equiv of [HNMe2Ph][B(C6F5)4], 4 is found to catalyze the hydrogenation of 1-hexene and also the polymerization of ethylene. Compounds 1−7 have been characterized by 1H NMR and IR spectroscopy, by microanalysis, and, in the case of 3, 4, and 7, by single-crystal X-ray diffraction studies. Cp*ThBr(OAr)2 (3) exhibits a somewhat distorted three-legged piano-stool geometry with Th−Cp*centroid, Th−O, and Th−Br distances of 2.57(1), 2.16(1) (av), and 2.821(2) Å, respectively. Cp*Th(OAr)(CH2SiMe3)2 (4) also displays a three-legged piano-stool geometry with Th−C distances to the alkyl groups of 2.460(9) and 2.488(12) Å. Th−Cp*centroid and Th−O distances are very similar to those found in 3, at 2.53(1) and 2.186(6) Å, respectively. Cp*Th(OC6H3-t-BuCMe2CH2)(OAr)(OPPh3) (7) features a distorted trigonal bipyramidal geometry about the metal center, with the Cp* ligand and the oxygen atom of the cyclometalated aryloxide ligand occupying axial sites (Cp*centroid−Th−O = 168.3(3)°). The Th−C distance to the tert-butyl methylene group is 2.521(12) Å, while Th−O distances to the aryloxide and triphenylphosphine oxide ligands are 2.199(7) (av) and 2.445(7) Å, respectively.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Mono(pentamethylcyclopentadienyl)thorium Chemistry: Synthesis, Structural Characterization, and Reactivity of Aryloxide and Alkyl Derivatives

et al. 1996

View full text Add to dashboard Cite

show abstract

“…The mixed-valent charge-transfer compound [Na(THF) 6 ][Cp*U(BH 4 ) 3 ] 2 was unexpectedly isolated from the reaction of U(BH 4 ) 3 (THF) x with Cp* 2 Th(PPh 2 ) 2 . In the crystal structure, the geometrical parameters are not significantly different in the independent Cp*U(BH 4 ) 3 moieties; the BH 4 ligands are tridentate …”

Section: Cyclopentadienyl Complexesmentioning

confidence: 92%

Synthesis, Structure, and Reactions of Hydride, Borohydride, and Aluminohydride Compounds of the f-Elements

1997

View full text Add to dashboard Cite

“…A borohydride anionic compound of trivalent uranium, showing very similar distances and angles, was also described. [25] The formal stoichiometry of 1 is Cp Ã0 Sm 2 X 5 ðTHFÞ 5 (X = BH 4 ). To our knowledge, the same overall stoichiometry has been reported only on one occasion, for the Sm(III) complex with X = Cl: ½CpðTHFÞ 2 SmCllCl 2 SmCl 2 ðTHFÞ 3 but the structure of this last complex is different.…”

mentioning

confidence: 99%

Structural diversity in the borohydrido lanthanides series: First isolation and X-ray crystal structure of ionic

Bonnet

Visseaux

Hafid

et al. 2007

Inorganic Chemistry Communications

View full text Add to dashboard Cite

Structural diversity in the borohydrido lanthanides series:First isolation and X-ray crystal structure of ionic ½SmðBH 4 Þ 2 ðTHFÞ 5 þ ½Cp Ã0 SmðBH 4 Þ 3 À AbstractThe reaction of SmðBH 4 Þ 3 ðTHFÞ 3 with a half equivalent of KCp Ã0 ðCp Ã0 ¼ C 5 Me n 4 Pr) affords a compound comprising one Cp Ã0 ligand and three THF molecules per two Sm atoms, ½Cp Ã0 Sm 2 ðBH 4 Þ 5 ðTHFÞ 3 , according to analytical data. Crystals of penta-THF adduct 1, showing the same 1 H NMR spectrum except for the quantity of THF, could be isolated from a solution of half-samarocene Cp Ã0 SmðBH 4 Þ 2 ðTHFÞ (2). X-ray structure determination of 1 revealed an ionic compound ½SmðBH 4 Þ 2 ðTHFÞ 5 þ ½Cp Ã0 SmðBH 4 Þ 3 À with two discrete mononuclear Sm polyhedrons. The expected neutral samarocene Cp Ã0 2 SmðBH 4 ÞðTHFÞ(3) could be obtained from the reaction of SmðBH 4 Þ 3 ðTHFÞ 3 with two equivalents of KCp Ã0 . X-ray structure analysis showed that 3 is a monomeric complex bearing a terminal borohydride ligand. All BH À 4 ligands in 1 and 3 exhibit an g 3 -H 3 BH bonding mode.

show abstract

Tetrahydroborate complexes of uranium: Preparation and crystal structure of mixed-valent [Na(THF)6] [(C5Me5)U(BH4)3]2

Cited by 18 publications

References 20 publications

Mono(pentamethylcyclopentadienyl)thorium Chemistry: Synthesis, Structural Characterization, and Reactivity of Aryloxide and Alkyl Derivatives

Mono(pentamethylcyclopentadienyl)thorium Chemistry: Synthesis, Structural Characterization, and Reactivity of Aryloxide and Alkyl Derivatives

Synthesis, Structure, and Reactions of Hydride, Borohydride, and Aluminohydride Compounds of the f-Elements

Structural diversity in the borohydrido lanthanides series: First isolation and X-ray crystal structure of ionic

Contact Info

Product

Resources

About