Derivatisation of boryl substituted titanium half-sandwich complexes – Molecular structures of [Ti{(η5-C5H4)B(NiPr2)N(H)tBu}Cl2(NMe2)] and [{TiCl2(μ-{OB(NHMe2)-η5-C5H4})}2-μ-O]

Braunschweig, Holger; Breitling, F.; Burschka, Christian; Seeler, Fabian

doi:10.1016/j.jorganchem.2005.10.008

Cited by 9 publications

(8 citation statements)

References 46 publications

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“…Other chemical groups have been introduced in place of the dimethylsilyl bridge, such as the phosphanyl-substituted cyclopentadienyl described by Lemenovskii et al [45] and the bridging boron derivative described by Braunschweig et al [36,[65][66][67] producing high molecular weight PE (see Table 1). …”

Section: Changing Bridge Zmentioning

confidence: 99%

How to synthesize a constrained geometry catalyst (CGC) – A survey

Cano

Kunz

2007

Journal of Organometallic Chemistry

104

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Section: Changing Bridge Zmentioning

confidence: 99%

How to synthesize a constrained geometry catalyst (CGC) – A survey

Cano

Kunz

2007

Journal of Organometallic Chemistry

104

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“…The presence of the cyclopentadienyl Cp ligands causes the coplanarity of the η 5 -C 5 Me 4 rings, as in [(TiCl 2 ) 2 (μ-{η 5 -C 5 R 4 SiMe 2 O} 2 )] (R = H, 36 Me 33 ), and also the elongation of the Ti-Ti distance, which is the longest found in complexes with a [Ti 2 (μ-{η 5 -C 5 Me 4 SiMeO} 2 )] moiety and also longer than in the analogous compound [(TiCl 2 ) 2 (μ-{(η 5 -C 5 H 4 B{NHMe 2 }O) 2 (μ-O)})]. 42 Reaction of 2as with LiMe. Alkylation of the isolated pure isomer 2as with LiMe in toluene did not give a unique compound but instead gave a mixture containing variable amounts of the three possible isomers of the dimethyl complexes [(TiMeCp) 2 (μ-{(η 5 -C 5 Me 4 SiMeO) 2 (μ-O)})] (3) (Scheme 2;…”

Section: Resultsmentioning

confidence: 93%

Dinuclear Dicyclopentadienyl Titanium Complexes with Bridging Cyclopentadienylsiloxo Ligands

et al. 2010

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Addition of 1 equiv of TlCp to compound [(TiCl 2 ) 2 (μ-{(η 5 -C 5 Me 4 SiMeO) 2 (μ-O)})] (A) at 80 °C gave a mixture with different molar ratios of the two possible isomers of [(TiClCp)(TiCl 2 )(μ-{(η 5 -C 5 Me 4 SiMeO) 2 (μ-O)})] (1). Reaction of compound A with 2 equiv of TlCp at 80 °C afforded [(TiClCp) 2 (μ-{(η 5 -C 5 Me 4 SiMeO) 2 (μ-O)})] (2as) as the unique reaction product. Each Cp ligand of 2as is located in different positions anti and syn with respect to the Si-O-Si bridge. However, a mixture of two isomers of [(TiClCp) 2 (μ-{(η 5 -C 5 Me 4 SiMeO) 2 (μ-O)})], 2as (>95% by NMR) and 2aa (<5% by NMR), was obtained when the reaction was carried out at 60 °C; the two Cp ligands of 2aa were located at anti positions. Alkylation of isomer 2as with LiMe gave a mixture of the three possible isomers [(TiMeCp) 2 (μ-{(η 5 -C 5 Me 4 SiMeO) 2 (μ-O)})] (3as, 3aa, 3ss). The proportion of each was dependent on the reaction temperature. Isomer 2as reacted with Lewis acids E(C 6 F 5 ) 3 (E=B, Al) and with Li[B(C 6 F 5 ) 4 ] to give the chloro-bridged dititanium compounds [(TiCp) 5aC and 5sC; Q=B(C 6 F 5 ) 4 ), with the remaining methyl ligand located at anti or syn positions depending on the methyl group being abstracted. DFT studies were carried out to determine the stability of the isomers of 2 and 3, to determine which chlorine atom in compound 2as was more easily eliminated, and also to clarify the transformation of isomer 2as into the mixture of isomers 3as, 3aa, and 3ss during the alkylation reaction. Article

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“…29 Further, the average B-O distance of 1.36(1) Å is also similar to those of the mentioned boroxide complexes but shorter than that reported for the dinuclear complex [{TiCl 2 (μ-{OB(NHMe 2 )-η 5 -C 5 H 4 })} 2 -μ-O] [1.486(3) Å ], where the boron and titanium atoms are also linked by a bridging oxygen atom (Table 6). 30 Conclusion A family of structurally novel adducts containing the preorganized ligands [{Ti(η 5 -C 5 Me 5 )} 3 (μ 3 -O)(μ 3 -CR)] (R = H, Me) and group 13 derivatives have been obtained. The new complexes locate the incorporated inorganic fragment on the periphery of the organometallic oxides and reveal how these trinuclear oxotitanium systems are also capable of acting as monodentate ligands.…”

Section: Resultsmentioning

confidence: 99%

Incorporation of Boron, Aluminum, and Gallium Derivatives into [{Ti(η⁵-C₅Me₅)(μ-O)}₃(μ₃-CR)] (R = H, Me)

et al. 2010

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The synthesis and characterization of a family of alkyl and halide adducts of group 13 elements (B, Al, Ga), containing the μ(3)-alkylidyne oxo derivative ligands [{Ti(η(5)-C(5)Me(5))(μ-O)}(3)(μ(3)-CR)] [R = H (1), Me (2)], are presented. The compounds are synthesized by Lewis acid-base reactions involving equimolecular amounts of 1 or 2 and alkyl [AlR'(3)] (R' = Me, Et, Ph) or halide derivatives [MX(3)] (M = B, X = Br; M = Al, X = Cl, Br, I; M = Ga, X = Cl, Br). The novel species [{E(3)M}(μ(3)-O)(μ-O)(2){Ti(η(5)-C(5)Me(5))}(3)(μ(3)-CR)] (3-8 and 11-21; R = H, Me; M = B, Al, Ga; E = alkyl, halide) exhibit coordination of 1 or 2 through one of the three oxygen atoms of the Ti(3)O(3) ring to the metal center. In the case of the reaction of 2 with 2 equiv of [AlMe(3)], the complex [{MeAl}(μ(3)-O)(3){Ti(η(5)-C(5)Me(5))}(3)(μ(3)-CCH(2-))] (9) containing the naked carbanion μ(3)-CCH(2-) was isolated with methane elimination. On the other hand, the derivative [{Br(3)B}(μ(3)-O)(μ-O)(2){Ti(η(5)-C(5)Me(5))}(3)(μ(3)-CMe)] (11) undergoes cleavage of the trinuclear structure to give [TiBr(η(5)-C(5)Me(5))}(μ-O){Ti(η(5)-C(5)Me(5))}(MeCBO(2)){TiBr(2)(η(5)-C(5)Me(5))}] (22). The crystalline structures of some of these products are also included in this paper.

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Derivatisation of boryl substituted titanium half-sandwich complexes – Molecular structures of [Ti{(η5-C5H4)B(NiPr2)N(H)tBu}Cl2(NMe2)] and [{TiCl2(μ-{OB(NHMe2)-η5-C5H4})}2-μ-O]

Cited by 9 publications

References 46 publications

How to synthesize a constrained geometry catalyst (CGC) – A survey

How to synthesize a constrained geometry catalyst (CGC) – A survey

Dinuclear Dicyclopentadienyl Titanium Complexes with Bridging Cyclopentadienylsiloxo Ligands

Incorporation of Boron, Aluminum, and Gallium Derivatives into [{Ti(η⁵-C₅Me₅)(μ-O)}₃(μ₃-CR)] (R = H, Me)

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Derivatisation of boryl substituted titanium half-sandwich complexes – Molecular structures of [Ti{(η5-C5H4)B(NiPr2)N(H)tBu}Cl2(NMe2)] and [{TiCl2(μ-{OB(NHMe2)-η5-C5H4})}2-μ-O]

Cited by 9 publications

References 46 publications

How to synthesize a constrained geometry catalyst (CGC) – A survey

How to synthesize a constrained geometry catalyst (CGC) – A survey

Dinuclear Dicyclopentadienyl Titanium Complexes with Bridging Cyclopentadienylsiloxo Ligands

Incorporation of Boron, Aluminum, and Gallium Derivatives into [{Ti(η5-C5Me5)(μ-O)}3(μ3-CR)] (R = H, Me)

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Incorporation of Boron, Aluminum, and Gallium Derivatives into [{Ti(η⁵-C₅Me₅)(μ-O)}₃(μ₃-CR)] (R = H, Me)