184899-34-1

Usage

InChI:InChI=1/C11H19NSi.2ClH.Zr/c1-11(2,3)12-13(4,5)10-8-6-7-9-10;;;/h6-9H,1-5H3;2*1H;/q-1;;;+3/p-2/rC11H19Cl2NSiZr/c1-11(2,3)14(16(12)13)15(4,5)10-8-6-7-9-10/h6-9H,1-5H3

Upstream product

• 159771-54-7 Zr(η(5)-C5H4SiMe2Cl)Cl3 
• 37828-54-9 lithium tert-butylamide 
• 75-77-4 chloro-trimethyl-silane 
• 174872-32-3 (tert-butyl-N-SiMe₂-cyclopentadienyl)Zr(NMe₂)2 
• 943987-58-4 Zr(NEt₂)4 

Relevant academic research and scientific papers

Stereoelectronic influence of the type of bifunctional ansa- monocyclopentadienyldimethylsilylamido ligand on the molecular structures displayed by zirconium dichloride and 1,4-diphenylbutadiene complexes

A series of organozirconium dichloride and 1,4-diphenylbutadiene complexes featuring a dianionic bifunctional ligand with a cyclopentadienyl-type functionality and an appended amido N donor have been prepared and structurally characterized. [(C5H4)SiMe2(N-t-Bu)]ZrCl 2, 1, [(C9H6)SiMe2(N-t-Bu)]ZrCl 2, 2, and [(C5Me4)SiMe2(N-i-Pr)] ZrCl2, 3, were prepared in two steps, with ligand chelation accomplished by an amine elimination reaction followed by treatment of the diamido Zr intermediate with an excess of SiMe3Cl. X-ray structural analyses reveal that in the solid state 2 is monomeric, whereas 1 and 3 are centrosymmetric dimers linked by a pair of bridging chlorides. The level of asymmetry displayed by the central Zr2(μ-Cl)2 moiety is indicated by the variation in the pair of independent bridging Zr-Cl bond distances, which are 2.618(1) and 2.657(1) A in 1 and 2.542(1) and 2.745(1) A in 3, respectively. The metathetical reactions of [Mg(C 4H4Ph2)(THF)3]n with 1, 2, 3, and [(C5Me4)SiMe2(N-t-Bu)]ZrCl 2 proceed to afford the corresponding 1,4-diphenylbutadiene derivatives 4, 5, 6, and 7, respectively. Solution NMR data show that 6 is obtained exclusively as the supine isomer, whereas compounds 4, 5, and 7 exist as >20:1, 6:1, and 2:1 mixtures of the supine and prone isomers at ambient temperature. The molecular structures of the supine forms of 4, 5, 6, and 7 are appreciably folded (70-80°) along the line of intersection between the plane containing the Zr and the two terminal butadiene carbons and the plane of the cis-butadiene fragment. An increase in the folding is accompanied by a decrease in the difference between the average Zr-C(terminal) and Zr-C(internal) bond distances and leads to a more pronounced long-short-long C-C bond sequence within the coordinated butadiene.

Mono- and di-cyclopentadienyl zirconium derivatives containing the dimethylsilylcyclopentadienyl ligand. Agostic linear Si-H-Zr interaction in the molecular structure of [Zr{η5-C5H4-(SiMe2H)}Cl3 ]2

Dimethylsilyl substituted mono- and di-cyclopentadienyl zirconium chlorides have been prepared and their reactions with amido and alkyl reagents studied. The silylcyclopentadienes C5H5(SiMe2H) 1, C5H4(SiMe2H)2 2 and C5H4(SiMe3)(SiMe2H) 3 can be prepared by reaction of Na(C5H5) with the appropriate chlorosilane reagent. The lithium salt Li[C5H4(SiMe2H)] reacts with ZrCl4 or [Zr(C5H5)Cl3] to give the metallocene complexes [Zr(C5H4R) {C5H4(SiMe2H)} Cl2] (R = SiMe2H 4 or H 5) whereas the reaction of the disilylcyclopentadiene C5H4(SiMe2H)2 with ZrCl4 afforded the monocyclopentadienyl complex [Zr {C5H4(SiMe2H)} Cl3] 6, which exchanges the Si-H and Zr-Cl bonds. The reaction of 6 with lithium amides produces different products depending on the basicity of the nitrogen atom and the steric demands of its amido substituents. The reaction with LiN(SiMe3)2 and LiNH(2,6-Me2C6H3) afforded the corresponding amido zirconium complexes [Zr{C5H4-(SiMe2H)}(NRR′)Cl2] (R = R′ = SiMe3 7; R = H, R′ = 2,6-Me2C6H3 8), but in the case of the reaction with LiNHtBu the known cyclopentadienylsilylamido derivative [Zr(η5,η1-C5H4SiMe2 NtBu)Cl2] was formed. The monoamido, diamido and dialkyl dicyclopentadienyl complexes [Zr(C5H4R) {C5H4(SiMe2H)} X(Y)] (R = SiMe2H 9 or H 10, X = C1, Y = NHtBu; R = SiMe2H 11 or H 12, X = Y = NHtBu; R = SiMe2H 13 or H 14, X = Y = Me) have been synthesized by reaction of 4 and 5 with the appropriate amido or methyl reagent. Compound 9 reacts with a stoichiometric amount of water with selective hydrolysis of the Zr-amido bond to give the corresponding μ-oxo dinuclear complex [{ Zr[C5H4(SiMe2H)]2Cl}2( μ-O)] 15. The molecular structure of [Zr{C5H4(SiMe2H)} Cl3] 6 was established by X-ray crystallography. Compound 6 is a dimer, in the solid state, in which dimerization occurs through Zr-H-Si agostic interactions and two chloride bridges.

Synthese, Charakterisierung und Polymerisationseigenschaften verbrueckter Halbsandwichkomplexe des Titans, Zirconiums und Hafniums; Die Molekuelstruktur von [C13H8-SiMe2-NtBu]ZrCl2

The synthesis of new ansa halfsandwich complexes of the type [Cp#-SiMe2-NtBu]MCl2 (Cp#=C13H8, C9H6, C5H4, C5H3tBu; M=Zr, Hf) as catalyst precursors for the polymerization of ethylene is described. The complexes were characterized by 1H-, 13C-, 29Si-, 15N- and 14N-NMR spectroscopy. From [C13H8-SiMe2-NtBu]ZrCl2 an X-ray structure was obtained. The activities of the catalysts and the properties of the polymers were investigated. The influence of the catalyst structure on the polymerization behaviour is discussed.

Synthesis and reactivity of [(amidosilyl)cyclopentadienyl]titanium and -zirconium complexes. X-ray molecular structure of [Zr{η5:η1-C5H4SiMe 2(μ-O)}Cl2{H2N(CHMe)Ph}]2

New half-sandwich (amidosilyl)cyclopentadienyl complexes of titanium(IV) and zirconium-(IV) were synthesized from the chlorosilyl-substituted cyclopentadienyl precursors [M(η5-C5H4SiMe2Cl)Cl 3] (M = Ti (1a), Zr (1b)). The reaction of [Ti(η5-C5H4SiMe2Cl)Cl 3] (1a) with LiNHR in the presence of NEt3 gives the [Ti(η5:η1-C5H4SiMe 2NR)Cl2] (R = tBu (2a), (±)-CH(Me)Ph (3a)) complexes. Similarly, the addition of 2 equiv of LiN(SiMe3)2 to complex 1a affords the diamido derivative [Ti(η5-C5H4SiMe 2Cl)Cl{N(SiMe3)2}2] (4a). The amidotitanium complex [Ti(η5:η1-C5H4SiMe 2NHtBu)Cl2(NHtBu)] (5a) is prepared, in low yield, by reacting 1a with NH2tBu in a 1:3 molar ratio. In this reaction, the presence of 2a is also detected. The same complexes 2a and 3a may also be obtained by reaction of the trichloro compound 1a with NH2R and NEt3 in a 1:1:2 molar ratio. The reaction of 2a with Tl(C5H5) gives the mixed-dicyclopentadienyl derivative [Ti(η5:η1-C5H4SiMe 2NtBu)(η5-C5H5)Cl] (6a). The dialkyl derivatives [Ti(η5:η1-C5H4SiMe 2NR)R′2] (R = tBu, R′ = CH3 (7a), CH2Ph (8a); R = CH(Me)-Ph, R′ = CH3 (9a), CH2Ph (10a)) have been isolated by reaction of 2 equiv of MgClMe or 1 equiv of Mg(CH2Ph)2·2THF with the dichlorides 2a and 3a. The analogous reaction of 2a with 1 equiv of MgCl(CH2Ph) affords the chloro alkyl derivative [Ti(η5:η1-C5H4SiMe 2NtBu)-(CH2Ph)Cl] (11a). The reaction of complexes 2a and 3a with CO2 leads to their conversion into the reported oxo derivative [Ti(μ-(η5:η1-C5H 4SiMe2O)}Cl2]2 with elimination of alkyl isocyanate O=C=NR (R = tBu, (±)-CH(Me)Ph) as the unique organic product. Addition of 1 equiv of LiN(SiMe3)2 to a diethyl ether solution of [Zr(η5:η1-C5H4SiMe 2Cl)Cl3] (1b) gives the monoamido derivative [Zr(η5:η1-C5H4SiMe 2Cl)Cl2{N(SiMe3)2}] (2b). The related reaction of the zirconium derivative 1b with LiNHtBu in the presence of NEt3 produces a mixture of two compounds, [Zr(η5:η1-C5H4SiMe 2NtBu)Cl2] (3b) and [Zr(η5-C5H4SiMe2NH tBu)Cl3(NEt3)] (4b). Pure 3b can be isolated by recrystallization of this mixture, but attempts to isolate the pure compound 4b were unsuccessful. The analogous reaction of 1b with 1 equiv of LiNHCH-(Me)Ph in the presence of NEt3 gives the related zirconium compound [Zr{η5:η1-C5H4SiMe 2-[NH(CHMe)Ph]}Cl3(NEt3)] (5b), which cannot be obtained as an analytically pure solid and is identified by 1H NMR spectroscopy. When water-saturated toluene is used to prepare 5b, the oxo-zirconium derivative [Zr{η5:η1-C5H4SiMe 2(μ-O)}Cl2{H2N(CHMe)Ph}]2 (6b) is obtained by slow precipitation. Compound 6b has been characterized by X-ray crystallography.