Quinolylcyclopentadienylthallium: A Donor-Stabilized Thallium(I) Compound

Enders, Markus; Fink, Jochen; Pritzkow, Hans

doi:10.1002/1099-0682(200009)2000:9<1923::aid-ejic1923>3.0.co;2-7

Cited by 14 publications

(3 citation statements)

References 10 publications

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“…The thallium−nitrogen(4) distance (2.868(1) Å) is shorter than those found for Tl−N(2), 3.190(1) Å, and Tl−N(3), 3.152(1) Å, which are in front of the cyclopentadienyl ligand. The thallium−nitrogen bond lengths compare well with those found in the literature for other structures bearing weak Tl−N interactions and are within the sum (3.47 Å) of the van der Waals radii of thallium and nitrogen . The cyclopentadienyl ligand is bonded in an η 5 fashion to thallium with a Tl(1)−Cp(centroid) distance of 2.687 Å, in the range observed for other crystalline cyclopentadienyl-containing Tl complexes. , Within the neutral ligand [(μ-NH) 3 Ti 3 (η 5 -C 5 Me 5 ) 3 (μ 3 -N)] there is not any important distortion in bond lengths and angles when compared with 1 .…”

Section: Resultssupporting

confidence: 80%

Coordination of [{Ti(η⁵-C₅Me₅)(μ-NH)}₃(μ₃-N)] to Metal Cyclopentadienides: Cyclopentadienyl Azaheterometallocubanes

et al. 2004

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Treatment of [{Ti(η5-C5Me5)(μ-NH)}3(μ3-N)] with lithium and sodium cyclopentadienide complexes [M(C5H5)] in toluene gives cube-type adducts [(η5-C5H5)M{(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}]. The reaction with thallium(I) cyclopentadienide in toluene affords the analogous [(η5-C5H5)Tl{(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}]·C7H8, whereas in hexane it gives [(η5-C5H5)Tl(μ-C5H5)Tl{(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}].

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Section: Resultssupporting

confidence: 80%

Coordination of [{Ti(η⁵-C₅Me₅)(μ-NH)}₃(μ₃-N)] to Metal Cyclopentadienides: Cyclopentadienyl Azaheterometallocubanes

et al. 2004

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“…Each sodium atom is coordinated by two Cp rings, one nitrogen atom of a quinolyl moiety, and one thf molecule. For quinolyl-substituted Cp complexes such a chain structure was first found in the case of the thallium compound [Tl 1b ] n . Chain structures are also known from various alkali metal cyclopentadienide salts. , A potassium compound of a donor-functionalized Cp ligand crystallizes also as a polymer chain with the five-membered ring, the donor group, and an additional molecule thf coordinated to the metal center …”

Section: Resultsmentioning

confidence: 97%

Synthesis of Main Group and Transition Metal Complexes with the (8-Quinolyl)cyclopentadienyl Ligand and Their Application in the Polymerization of Ethylene

2004

Self Cite

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Nucleophilic addition of 8-lithioquinoline to the Cp 2 Co + cation leads to the formation of η 4 -(8-quinolylcyclopentadiene)(η 5 -cyclopentadienyl)cobalt(I) (7). Oxidative decomplexation with FeCl 3 liberates the quinolyl-substituted cyclopentadiene derivative 2a, which is stable at low temperature only. Deprotonation by strong bases such as NaH or KH leads to the alkali metal quinolyl cyclopentadienide salts, which are used as precursors for the synthesis of the corresponding Ti, Cr, and Al complexes. Whereas after its activation the aluminum compound 13 does not yield an olefin polymerization catalyst, the chromium(III) complex 12 reacts with methylaluminoxane (MAO) to give a highly active catalyst for the polymerization of ethylene.

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“…A search for intermolecular contacts between Tl···C at a distance of 2.0 and 3.0 Å in the Cambridge database led to a series of Tl···C π-interactions with cyclopentadienyl (Cp) ligands. − The Tl−C distances typically involve the Tl−Cp ring and range from 2.735 to 2.973 Å. − A Tl−π-arene interaction was observed for a Tl[9-(1-cyclopentadienyl-1-methylethyl) fluorenyl] complex . In this structure, the Tl metal center is bound to a cyclopentadienyl ligand as well as the π-arene ring of the side group.…”

Section: Resultsmentioning

confidence: 99%

From Clusters to Ionic Complexes: Structurally Characterized Thallium Titanium Double Alkoxides

Boyle¹,

Zechmann²,

Alam³

et al. 2002

Inorg. Chem.

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A series of sterically varied titanium alkoxides [[Ti(OR)(4)](n)(), n = 4, OR = OCH(2)CH(3) (OEt); n = 1, OCH(CH(3))(2) (OPr(i)); n = 2, OCH(2)C(CH(3))(3) (ONep); n = 1, OC(6)H(3)(CH(3))(2)-2,6 (DMP)] were reacted with a series of thallium alkoxides [[Tl(OR)](x) (x = 4, OR = OEt, ONep; n = infinity, DMP)]. The resultant products of the [Tl(mu(3)-OEt)](4)-modified [Ti(OR)(4)](n)() (OR = OEt, OPr(i), ONep) were found by X-ray analysis to be Tl(4)Ti(2)(mu-O)(mu(3)-OEt)(8)(OEt)(2) (1), Tl(4)Ti(2)(mu-O)(mu(3)-OPr(i))(5)(mu(3)-OEt)(3)(OEt)(2) (2), and TlTi(2)(mu(3)-OEt)(2)(mu-OEt)(mu-ONep)(2)(ONep)(4) (3), respectively. The reaction of [Tl(mu(3)-OEt)](4), 12HOEt, and 4[Ti(mu-ONep)ONep)(3)](2) to generate 3 in a higher yield resulted in the isolation of TlTi(2)(mu(3)-OEt)(mu(3)-ONep)(mu-OEt)(mu-ONep)(2)(ONep)(4) (4). Compounds 1 and 2 possess an octahedral (Oh) arrangement of two Ti and four Tl metal atoms around a mu-O central oxide atom (the Tl-O distance is too long to be considered a bond). For both compounds, each Ti atom adopts a distorted Oh geometry with one terminal OEt ligand. The Tl atoms are formally 4-coordinated, adopting a distorted pyramidal geometry using four mu(3)-OR (OR = OEt or OPr(i)) ligands to complete their coordination sphere. The Tl atoms reside approximately 1.4 A below the basal plane of oxygens. In contrast to these structures, both 3 and 4 utilize ONep ligands and display reduced oligomerization yielding trinuclear complexes without oxo formation. The two Ti cations are Oh, and the single Tl cation is in a formal distorted pyramidal (PYD) arrangement. If the lone pair of the Tl cations are considered in the geometry, each Tl adopts a square base pyramidal geometry. Two terminal ONep ligands are bound to each Ti with the remainder of the molecule consisting of mu(3)- and mu-ONep ligands. The reaction of [Tl(mu(3)-ONep)](4) with two equivalents of [Ti(mu-ONep)(ONep)(3)](2) also led to the isolation of the homoleptic trinuclear complex TlTi(2)(mu(3)-ONep)(2)(mu-ONep)(3)(ONep)(4) (5) which is analogous in structure to the mixed ligand species of 3 and 4. Each Ti is Oh coordinated with six ONep ligands, and the single Tl is PYD bound by ONep ligands. A further increase in the steric bulk of the pendant ligands, using [Tl(mu-DMP)](infinity) and [Ti(mu-ONep)(ONep)(3)](2), resulted in a further decrease in the nuclearity yielding the dinuclear species TlTi(mu-DMP)(mu-ONep)(DMP)(ONep)(2) (6). For 6, the two metals are bound by a mu-ONep and a mu-DMP ligand. The Tl metal center was solved in a bent geometry while the Ti adopted a distorted trigonal bipyramidal (TBP) geometry using three ONep and two DMP ligands to fill its coordination sphere. Further increasing the steric bulk of the ancillary ligands using Ti(DMP)(4) and [Tl(mu-DMP)](infinity) led to the formation of [Tl(+)][(-)(eta(2-3)-DMP)Ti(DMP)(4)] (7). The Ti metal center is in a TBP geometry, and the "naked" Tl cation resides unencumbered by solvent molecules but was found to have a strong pi-interaction with four DMP ligands of neighboring...

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Quinolylcyclopentadienylthallium: A Donor-Stabilized Thallium(I) Compound

Cited by 14 publications

References 10 publications

Coordination of [{Ti(η⁵-C₅Me₅)(μ-NH)}₃(μ₃-N)] to Metal Cyclopentadienides: Cyclopentadienyl Azaheterometallocubanes

Coordination of [{Ti(η⁵-C₅Me₅)(μ-NH)}₃(μ₃-N)] to Metal Cyclopentadienides: Cyclopentadienyl Azaheterometallocubanes

Synthesis of Main Group and Transition Metal Complexes with the (8-Quinolyl)cyclopentadienyl Ligand and Their Application in the Polymerization of Ethylene

From Clusters to Ionic Complexes: Structurally Characterized Thallium Titanium Double Alkoxides

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Quinolylcyclopentadienylthallium: A Donor-Stabilized Thallium(I) Compound

Cited by 14 publications

References 10 publications

Coordination of [{Ti(η5-C5Me5)(μ-NH)}3(μ3-N)] to Metal Cyclopentadienides: Cyclopentadienyl Azaheterometallocubanes

Coordination of [{Ti(η5-C5Me5)(μ-NH)}3(μ3-N)] to Metal Cyclopentadienides: Cyclopentadienyl Azaheterometallocubanes

Synthesis of Main Group and Transition Metal Complexes with the (8-Quinolyl)cyclopentadienyl Ligand and Their Application in the Polymerization of Ethylene

From Clusters to Ionic Complexes: Structurally Characterized Thallium Titanium Double Alkoxides

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Coordination of [{Ti(η⁵-C₅Me₅)(μ-NH)}₃(μ₃-N)] to Metal Cyclopentadienides: Cyclopentadienyl Azaheterometallocubanes

Coordination of [{Ti(η⁵-C₅Me₅)(μ-NH)}₃(μ₃-N)] to Metal Cyclopentadienides: Cyclopentadienyl Azaheterometallocubanes