cas 19756-04-8, TETRAKIS(DIMETHYLAMINO)ZIRCONIUM

Articles about 19756-04-8Total 15 be found

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Amide-silyl ligand exchanges and equilibria among group 4 amide and silyl complexes
M(NMe2)4 (M = Zr, 1a; Hf, 1b) and the silyl anion (SiButPh2)- (2) in Li(THF)2SiBu tPh2 (2-Li) were found to undergo a ligand exchange to give [M(NMe2)3(SiButPh2) 2]- (M = Zr, 3a; Hf, 3b) and [M(NMe2) 5]- (M = Zr, 4a; Hf, 4b) in THF. The reaction is reversible, leading to equilibria: 2 1a (or 1b) + 2 2 ? 3a (or 3b) + 4a (or 4b). In toluene, the reaction of 1a with 2 yields [(Me2N) 3Zr(SiButPh2)2] -[Zr(NMe2)5Li2(THF) 4]+ (5) as an ionic pair. The silyl anion 2 selectively attacks the -N(SiMe3)2 ligand in (Me2N) 3Zr-N(SiMe3)2 (6a) to give 3a and [N(SiMe 3)2]- (7) in reversible reaction: 6a + 2 2 ? 3a + 7. The following equilibria have also been observed and studied: 2M(NMe2)4 (1a; 1b) + [Si(SiMe3) 3]- (8) ? (Me2N)3M-Si(SiMe 3)3 (M = Zr, 9a; Hf, 9b) + [M(NMe2) 5]- (M = Zr, 4a; Hf, 4b); 6a (or 6b) + 8 ? 9a (or 9b) + [N(SiMe3)2]- (7). The current study represents rare, direct observations of reversible amide-silyl exchanges and their equilibria. Crystal structures of 5, (Me2N)3Hf- Si(SiMe3)3 (9b), and [Hf(NMe2) 4]2 (dimer of 1b), as well as the preparation of (Me 2N)3M-N(SiMe3)2 (6a; 6b) are also reported.
Cai, Hu,Yu, Xianghua,Chen, Shujian,Qiu, He,Guzei, Ilia A.,Xue, Zi-Ling
p. 8071 - 8078
(2007)
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Zirconium and titanium amido complexes with 3,3-dimethyl-1,5-diaza-S- oxacyclodecane; facile C-H activation of the macrocyclic rim
Reaction of the dilithium salt of 3,3-dimethyl-1,5-diaza-8-oxacyclodecane, [(NLi)2O], with Zr(NEt2)2Cl2(thf) 2 gave the formally 20e- complex [Zr(N2O) 2]; metallation
Porter, Robin M.,Danopoulos, Andreas A.,Reid, Gillian,Titcomb, Lisa R.
p. 427 - 428
(2005)
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Fabrication and characterization of ALD-grown ZrO2:Ge thin films on Si(100) using CpZr(NMe2)3 and (NMe2)2Ge(ipr2en) precursors with ozone
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Jung, Jae-Sun,Kim, Dae-Hyun,Shin, Jin-Ho,Kang, Jung-Soo,Thomas, Joseph P.,Leung,Kang, Jun-Gill
p. 2162 - 2165
(2015)
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Immobilization of η5-cyclopentadienyltris(dimethylamido) zirconium polymerization catalysts on a chlorosilane- and HMDS-modified mesoporous silica surface: A new concept for supporting metallocene amides towards heterogeneous single-site-catalysts
The modification of a mesoporous silica surface with Si(Ind)(CH3)2Cl and the immobilization of CpZr(NMe2)3 on this surface was studied via IR-spectroscopy. To reduce side reactions, the indenyl-modified silica was reacted with hexamethyldisilazane (HMDS) under IR-control before the CpZr(NMe2)3-immobilization. The role of the hydroxyl group protection with HMDS is discussed. The surface modifications have been repeated via Schlenk technique at the same conditions and the surface modifications were studied with 13C CP MAS-NMR, 1H MAS-NMR, elemental-, SEM- and BET-analysis. The surface species of the resulting catalysts are discussed. The precatalysts have been treated with methylaluminoxane (MAO) (Al:Zr (mol:mol) = 500:1) and the resulting Zr contents (leaching-effect) are discussed. All catalysts have been tested in ethylene and propylene polymerization.
Schneider, Horst,Puchta, Gerd T,Kaul, Franz A.R,Raudaschl-Sieber, Gabriele,Lefebvre, Frédéric,Saggio, Guillaume,Mihalios, Dimitrios,Herrmann, Wolfgang A,Basset, Jean Marie
p. 127 - 141
(2001)
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Efficient synthesis of rac-(ethylenebis(indenyl))ZrX2 complexes via amine elimination
The amine elimination reaction of 1,2-bis(3-indenyl)ethane (3) and Zr(NMe2)4 (2) affords pure rac-(EBI)Zr(NMe2)2 (4; EBI = 1,2-ethylenebis(1-indenyl)) in 68% isolated yield. Treatment of 4 with 2 equiv of Me2-NH·HCl affords rac-(EBI)ZrCl2 (1) in 92% isolated yield. Compound 1 can also be prepared directly from 2 and 3 in a one-pot synthesis in 69% isolated yield.
Diamond, Gary M.,Rodewald, Stephan,Jordan, Richard F.
p. 5 - 7
(1995)
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Synthesis and Characterization of Group 4 Amido Silyl Complexes Free of Anionic π-Ligands
A series of early-transition-metal silyl complexes free of anionic π-ligands such as cyclopentadienyl (Cp = η5-C5H5) have been synthesized. These Cp-free complexes (Me2N)3MSi(SiMe3)3 [M = Zr (1), Hf (2)], (Me2N)3TiSiPh2But (3), (Me2N)3ZrSiPh2But·0.5THF (4), (Me2N)3HfSiPh2But·nTHF [n = 0.5 (5a), 1 (5b)], and (Me2N)2[(Me3Si)2N]ZrSiR3 [SiR3 = Si(SiMe3)3 (7), SiPh2But (8)] were prepared by metathetic reactions of chloro triamido complexes (Me2N)3MCl (M = Ti, Zr, Hf) or (Me2N)2[(Me3Si)2N]ZrCl (6) with silyllithium reagents Li(THF)3Si(SiMe3)3 or Li(THF)3SiPh2But. The structures of 1, 3, 4, 5b, and 8 have been determined by X-ray crystallography and show that 1, 3, and 8 adopt a distorted tetrahedral coordination geometry while 4 and 5b have a distorted trigonal bipyramidal geometry around the metal. The unit cell parameters are as follows. 1: space group R3c, a = 15.505(2) A?, c = 19.308(4) A?, V = 4019.9(13) A?3, Z = 6. 3: space group P21, a = 8.633(5) A?, b = 14.790(7) A?, c = 9.388(4) A?, β = 92.44(4)°, V = 1197.6(10) A?3, Z = 2. 4: space group Pbca, a = 16.538(9) A?, b = 17.282(7) A?, c = 18.566(8) A?, V = 5306(4) A?3, Z = 8. 5b: space group Pna21, a = 17.463(6) A?, b = 9.453(3) A?, c = 17.800(6) A?, V = 2938(2) A?3, Z = 4. 8: space group Pca21, a = 19.775(5) A?, b = 10.182(2) A?, c = 15.752(5) A?, V = 3172(2) A?3, Z = 4. The M-Si bond distances for 1, 3, 4, 5b, and 8 are 2.781(2), 2.635(2), 2.803(2), 2.807(4), and 2.860(2) A?, respectively. The Zr-Si bond in 8, to our knowledge, is the longest reported Zr-Si bond.
Wu, Zhongzhi,Diminnie, Jonathan B.,Xue, Ziling
p. 6366 - 6372
(1998)
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Structurally characterized carboxylic acid modified zirconium alkoxides for the production of zirconium oxide thin films
A series of carboxylic acid (H-ORc) modified zirconium alkoxides (Zr(OR)4) were synthesized through the reaction of the commercially available [Zr(μ-OPri)(OPri)3(H-OPr i)]2 (1, OPri = OCH(CH3) 2) with a series of sterically varied H-ORc, including: formic acid (H-O2CH or H-OFc), acetic acid (H-O2CCH3 or H-OAc), isobutyric acid (H-O2CCH(CH3)2 or H-OPc), trimethyl acetic acid (H-O2C(CH3)3 or H-OBc), and t-butyl acetic acid (H-O2CCH2C(CH 3)3 or H-ONc) which yielded the following products: Zr4(μ4-O)(μ-O)(μ-OFc)2(μ-OPr i)4(OPri)6 (2), Zr 3(μ3-O)(μ-OAc)3(OAc)2(μ- OPri)2(OPri)3 (3), [Zr 2(μ-OPc)2(μ-OPri)2(OPr i)4]2 (4), Zr2(μ-OBc)(μ- OPri)2(OPri)5(H-OPri) ? (H-OPri) (5), Zr2(μ-ONc)(ONc)(μ-OPr i)2(OPri)4(H-OPri) (6).To increase the structural variability of these precursors, we also investigated the H-ORc modifications of the novel Zr3(μ3-O) (μ3-ONep)(μ-ONep)3(ONep)6 (7) which was isolated from the reaction between Zr(NMe2)4 and 4 H-OCH2C(CH3)3 (H-ONep).The ORc-modified 7 species were isolated as: Zr3(μ3-O)(μ-OAc) 3(μ-ONep)2(ONep)5 (8), Zr 5(μ-O)3(μ-OPc)6(μ-ONep) 2(ONep)6 (9), [Zr(μ-OPc)(μ-ONep)(ONep) 2]2 (10), Zr5(μ-O)3(μ-ONc) 6(μ-ONep)2(ONep)6 ? (H-ONep) ? 1/2(C7H8) (11). Once fully characterized, these compounds were used to generate thin films of ZrO2 to investigate the optimal structural aspects that dictate thin film density. It was determined that the majority of these compounds did not yield high quality films; however, the non-condensed species (3-5) did produce clear and continuous ZrO2 films. From this very limited set of useful precursors, the larger nuclearity species (3) led to films of higher densification.
Boyle, Timothy J.,Ottley, Leigh Anna M.,Rodriguez, Mark A.
p. 1727 - 1738
(2005)
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Novel precursor compounds for forming zirconium-containing film, compositions for forming zirconium-containing film comprising the same, and method of forming zirconium-containing film using them as precursors
Disclosed are a cyclopentadienyl zirconium (IV) compound which is substituted with a cycloalkyl group represented in the chemical formula 1, a precursor composition for forming a zirconium-containing film including the same, and a method for forming a zirconium-containing film by using the same. In the composition, the compound in the chemical formula 1 does not react with mixed components thereof and exists stably from each other and in a uniformly mixed state in a liquid state and therefore, the composition behaves as a single compound and shows a high vapor pressure. By using the composition of the present invention, it is possible to easily and economically obtain a zirconium-containing film having the same quality as a high quality zirconia.(AA) Chemical shiftCOPYRIGHT KIPO 2016
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Paragraph 0115-0117

(2016/10/17)

A method of manufacturing a zirconium compound
PROBLEM TO BE SOLVED: To provide a method for producing an industrially suitable zirconium amide compound by which the zirconium amide compound can be produced in high yield and high selectivity by using a zirconium halide as a starting material. SOLUTION: The method for producing the zirconium amide compound includes mixing the zirconium halide with a dialkylamine, and reacting the mixture, cyclopentadiene which may have a substituent, and an alkyl alkali metal. COPYRIGHT: (C)2013,JPOandINPIT
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Paragraph 0062-0064

(2016/12/22)

Mesoporous Silica-Supported Amidozirconium-Catalyzed Carbonyl Hydroboration
The hydroboration of aldehydes and ketones using a silica-supported zirconium catalyst is reported. Reaction of Zr(NMe2)4 and mesoporous silica nanoparticles (MSN) provides the catalytic material Zr(NMe2)n@MSN. Exhaustive characterization of Zr(NMe2)n@MSN with solid-state (SS)NMR and infrared spectroscopy, as well as through reactivity studies, suggests its surface structure is primarily ≡ SiOZr(NMe2)3. The presence of these nitrogen-containing zirconium sites is supported by 15N NMR spectroscopy, including natural abundance 15N NMR measurements using dynamic nuclear polarization (DNP) SSNMR. The Zr(NMe2)n@MSN material reacts with pinacolborane (HBpin) to provide Me2NBpin and the material ZrH/Bpin@MSN that is composed of interacting surface-bonded zirconium hydride and surface-bonded borane ≡ SiOBpin moieties in an approximately 1:1 ratio, as well as zirconium sites coordinated by dimethylamine. The ZrH/Bpin@MSN is characterized by 1H/2H and 11B SSNMR and infrared spectroscopy and through its reactivity with D2. The zirconium hydride material or the zirconium amide precursor Zr(NMe2)n@MSN catalyzes the selective hydroboration of aldehydes and ketones with HBpin in the presence of functional groups that are often reduced under hydroboration conditions or are sensitive to metal hydrides, including olefins, alkynes, nitro groups, halides, and ethers. Remarkably, this catalytic material may be recycled without loss of activity at least eight times, and air-exposed materials are catalytically active. Thus, these supported zirconium centers are robust catalytic sites for carbonyl reduction and that surface-supported, catalytically reactive zirconium hydride may be generated from zirconium-amide or zirconium alkoxide sites.
Eedugurala, Naresh,Wang, Zhuoran,Chaudhary, Umesh,Nelson, Nicholas,Kandel, Kapil,Kobayashi, Takeshi,Slowing, Igor I.,Pruski, Marek,Sadow, Aaron D.
p. 7399 - 7414
(2015/12/11)

ORGANOMETALLIC COMPOUND PREPARATION
A method of continuously manufacturing an organometallic compound is provided where two or more reactants are conveyed to a contacting zone of a reactor in a manner so as to maintain a laminar flow of the reactants; and causing the reactants to form the organometallic compound.
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Paragraph 0044; 0048; 0049

(2013/08/28)

ORGANOMETALLIC COMPOUND PREPARATION
A method of continuously manufacturing organometallic compounds is provided where two or more reactants are conveyed to a reactor having a laminar flow contacting zone, a heat transfer zone, and a mixing zone having a turbulence-promoting device; and causing the reactants to form the organometallic compound.
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Paragraph 0054; 0058; 0059

(2013/08/28)

A new scorpionate ligand: Tris(4,4-dimethyl-2-oxazolinyl)borate and its zirconium(IV) complexes
The first example of a new class of oxazoline-based scorpionate ligand, tris(4,4-dimethyl-2-oxazolinyl)phenyl borate, [ToM]-, is prepared by reaction of 2-lithio-4,4-dimethyl-2-oxazolide and 0.3 equiv of dichlorophenylborane. The steric bulk of this ligand is greater than that of tris(3,5-Me2-pyrazolyl)borate (Tp*), as quantified by comparison of solid angles of crystallographically characterized zirconium(IV) complexes.
Dunne, James F.,Su, Jiachun,Ellern, Arkady,Sadow, Aaron D.
p. 2399 - 2401
(2009/02/02)

Unusual Equilibria Involving Group 4 Amides, Silyl Complexes, and Silyl Anions via Ligand Exchange Reactions
Silyl anion SiButPh2- (2) was found to substitute an amide ligand in Zr(NMe2)4 (3) to give the disilyl complex Zr(NMe2)3(SiButPh2)2- (
Yu, Xianghua,Cai, Hu,Guzei, Ilia A.,Xue, Ziling
p. 4472 - 4473
(2007/10/03)

Organometallic compound, its synthesis method, and solution raw material and metal-containing thin film containing the same
The organometallic compound of the present invention is a compound that has bonds between metal atoms and nitrogen atoms or bonds between semimetal atoms and nitrogen atoms, and the content of chlorine in the compound is 200 ppm or less and the content of water is 30 ppm or less. In addition, the general formula of this compound is represented by the following formula (1): M[(R1)2N](n?s)(R2)s??(1) wherein, M represents a metal atom or semimetal atom, with the metal atom being Hf, Zr, Ta, Ti, Ce, Al, V, La, Nb or Ni, and the semimetal atom being Si, R1 represents a methyl group or ethyl group, R2 represents an ethyl group, n represents the valence of M, and s represents an integer of 0 to n?1.
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(2008/06/13)