Synthesis and structural characterization of the sandwichlike compound [(12-crown-4)Li(.eta.5-C5H5)] and the .eta.0-substituted-cyclopentadienide salt [Li(12-crown-4)2][1,2,4-(Me3Si)3C5H2]

Chen, H; Jutzi, Peter; Leffers, Wilhelm; Olmstead, M. M.; Power, P.

doi:10.1021/om00051a015

Cited by 49 publications

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“…Several structures of isolated cyclopentadienyl ligands are in the literature, 45−51 and the effect of Me 3 Si groups in providing "naked" cyclopentadienyls has been discussed. 50 The C−C and C−Si bond distances in 4 are similar to those in (LiCp′)·TMEDA 51 Figure 5, Scheme 7. The reaction is similar to the naphthalene reaction in Scheme 3, except that now a biphenyl dianion, (η 6 -C 6 H 5 Ph) 2− , is formed, as shown by the crystallographic data described below.…”

Section: ■ Experimental Sectionmentioning

confidence: 78%

Reactivity of the Ln²⁺ Complexes [K(2.2.2-cryptand)][(C₅H₄SiMe₃)₃Ln]: Reduction of Naphthalene and Biphenyl

2015

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The reductive capacity of the recently discovered Ln 2+ complexes [K(2.2.2-cryptand)][Cp′ 3 Ln], 1-Ln (Cp′ = C 5 H 4 SiMe 3 ; Ln = Y, La, Ce, Dy), has been probed by examining their reactions with aromatic hydrocarbons. [K-(2.2.2-cryptand)][Cp′ 3 Y], 1-Y, is capable of reducing naphthalene and forms a mixture of the naphthalenide dianion complex [K(2.2.2-cryptand)][Cp′ 2 Y(η 4 -C 10 H 8 )], 2-Y, as well as the ligand redistribution product [K(2.2.2-cryptand)][Cp′ 4 Y], 3-Y, and the cyclopentadienyl ligand salt [K(2.2.2-cryptand)]-[Cp′], 4. Naphthalene is reduced analogously by 1-La, 1-Ce, and 1-Dy. Each complex in the yttrium reaction was synthesized independently to confirm its identity in the mixture. Complex 2-Y was prepared from [Cp′ 2 Y(THF) 2 ]-[BPh 4 ], 5 (synthesized from [Et 3 NH][BPh 4 ] and Cp′ 3 Y), and K/naphthalene. Complex 3-Y was obtained by adding KCp′ to Cp′ 3 Y in the presence of 2.2.2-cryptand. [K(2.2.2-cryptand)][Cp′] was synthesized from 2.2.2-cryptand and KCp′. Each C 10 unit in the reduced naphthalene products, 2-Y, 2-La, 2-Ce, and 2-Dy, is bent with four carbon atoms of one ring oriented toward the metal, while the remaining six carbon atoms form a planar ring consistent with (η 4 -C 10 H 8 ) 2− coordination. In the solid state, 3-Y contains one η 1 -Cp′ ligand and three η 5 -Cp′ rings, whereas all four Cp′ rings in 3-La have η 5 -coordination. In the solid-state structure of 4, the (Cp′) − anion is not coordinated to potassium, which is encapsulated by the cryptand and located 7.063 Å from the ring centroid. Complex 1-Y also reduces biphenyl to form [K(2.2.2-cryptand)][Cp′ 2 Y(η 6 -C 6 H 5 Ph)], 6-Y, which contains a dianion with a planar aromatic phenyl ring as a substituent on a nonplanar η 6 -C 6 ring oriented toward the metal ion. ■ INTRODUCTIONRecently, the number of +2 ions available in the lanthanide series in soluble molecular complexes has been expanded from the traditional list of six, namely, Eu 2+ , Yb 2+ , Sm 2+ , Tm 2+ , Dy 2+ , and Nd 2+ , to the rest of the lanthanides except radioactive promethium via the potassium graphite reactions shown in Schemes 1 1 and 2. 2−4 The availability of these complexes allows the reaction chemistry of these new oxidation states to be investigated for the first time.A traditional way to characterize reducing agents too reactive for reproducible electrochemistry is to treat them with polycyclic hydrocarbons of known reduction potential. 5−8 This was initially used to characterize the reactivity 5 of (C 5 Me 5 ) 2 Sm 9 and subsequently used for NdI 2 6 and DyI 2 . 7 (C 5 Me 5 ) 2 Sm can reduce anthracene (−1.98 V vs SCE 10 ) to form [(C 5 Me 5 ) 2 Sm] 2 (μ-C 14 H 10 ), but it does not reduce naphthalene (−2.60 V vs SCE 10 ). 5 The stronger reductants, NdI 2 and DyI 2 , reduce naphthalene in 1,2-dimethoxyethane (DME) and THF to produce [NdI 2 (THF) 3 ] 2 (μ-C 10 H 8 ) 6 and (C 10 H 8 )DyI(DME) 2 , 7 respectively. Although other reduced naphthalene complexes of the rare earth ions are known, 8,11−18 their preparations involve either (a) initial...

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Section: ■ Experimental Sectionmentioning

confidence: 78%

Reactivity of the Ln²⁺ Complexes [K(2.2.2-cryptand)][(C₅H₄SiMe₃)₃Ln]: Reduction of Naphthalene and Biphenyl

2015

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“…The complexes of CpLi with PMDETA, TMEDA, and DME establish a coordination family analogous to the already known complex (η 5 -Cp)Li(12-crown-4). 12 In these complexes the Cp anion is η 5coordinated by a single lithium ion. The metal is 4-fold coordinated (1) and 3-fold-coordinated (2 and 3), respectively, by the ring center and the donor atoms (see d in Scheme 2).…”

Section: ' Results and Discussionmentioning

confidence: 99%

Revealing Coordination Patterns in C₅-Cyclic Lithium Organics

Michel

Herbst‐Irmer

2011

Organometallics

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“…The potassium ion is sandwiched between the crown ether and the deprotonated five-membered ring of the [HL 1 ] Ϫ anion; this is similar to the arrangement in [Li] ϩ [C 5 H 5 ] Ϫ ؒ12-crown-4 (12crown-4 = 1,4,7,10-tetraoxacyclododecane). 69 The unresolved disorder associated with the crown ether means that the details of its co-ordination to the potassium ion cannot be meaningfully discussed. The co-ordination of the potassium ion to the 1917, 1987 1888, 1962 1905, 1918, 1977 1913, 1980 1898, 1975 1892, 1966 1862, 1943 1866, 1945 1851, 1861, 1937 1863, 1941 1844, 1934 Ref.…”

Section: Crystal Structures Of Organometallic H 2 L 1 Derivativesmentioning

confidence: 99%

Synthesis and structures of organometallic derivatives of 1,2,3,4,5,6,7,8-octamethyl-1,5-dihydro-s-indacene

Barlow¹,

Cary²,

Drewitt³

et al. 1997

J. Chem. Soc., Dalton Trans.

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Synthesis and structural characterization of the sandwichlike compound [(12-crown-4)Li(.eta.5-C5H5)] and the .eta.0-substituted-cyclopentadienide salt [Li(12-crown-4)2][1,2,4-(Me3Si)3C5H2]

Cited by 49 publications

References 0 publications

Reactivity of the Ln²⁺ Complexes [K(2.2.2-cryptand)][(C₅H₄SiMe₃)₃Ln]: Reduction of Naphthalene and Biphenyl

Reactivity of the Ln²⁺ Complexes [K(2.2.2-cryptand)][(C₅H₄SiMe₃)₃Ln]: Reduction of Naphthalene and Biphenyl

Revealing Coordination Patterns in C₅-Cyclic Lithium Organics

Synthesis and structures of organometallic derivatives of 1,2,3,4,5,6,7,8-octamethyl-1,5-dihydro-s-indacene

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Synthesis and structural characterization of the sandwichlike compound [(12-crown-4)Li(.eta.5-C5H5)] and the .eta.0-substituted-cyclopentadienide salt [Li(12-crown-4)2][1,2,4-(Me3Si)3C5H2]

Cited by 49 publications

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Reactivity of the Ln2+ Complexes [K(2.2.2-cryptand)][(C5H4SiMe3)3Ln]: Reduction of Naphthalene and Biphenyl

Reactivity of the Ln2+ Complexes [K(2.2.2-cryptand)][(C5H4SiMe3)3Ln]: Reduction of Naphthalene and Biphenyl

Revealing Coordination Patterns in C5-Cyclic Lithium Organics

Synthesis and structures of organometallic derivatives of 1,2,3,4,5,6,7,8-octamethyl-1,5-dihydro-s-indacene

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Reactivity of the Ln²⁺ Complexes [K(2.2.2-cryptand)][(C₅H₄SiMe₃)₃Ln]: Reduction of Naphthalene and Biphenyl

Reactivity of the Ln²⁺ Complexes [K(2.2.2-cryptand)][(C₅H₄SiMe₃)₃Ln]: Reduction of Naphthalene and Biphenyl

Revealing Coordination Patterns in C₅-Cyclic Lithium Organics