19756-04-8

Basic information

• Product Name: TETRAKIS(DIMETHYLAMINO)ZIRCONIUM
• Synonyms: ZIRCONIUM TETRAKIS(DIMETHYLAMIDE);ZIRCONIUM DIMETHYLAMIDE;TETRAKIS(DIMETHYLAMIDO)ZIRCONIUM(IV);TETRAKIS(DIMETHYLAMINO)ZIRCONIUM;TETRAKIS(DIMETHYLAMINO)ZIRCONIUM(IV);TETRAKIS(DIMETHYLAMIDO)ZIRCONIUM(IV), 99.99+%, ELECTRONIC GRADE;TETRAKIS(DIMETHYLAMINO)ZIRCONIUM(IV) C&;Tetrakis(dimethylamino)zirkonium
• CAS NO: 19756-04-8
• Molecular Formula: 4C₂H₆N*Zr
• Molecular Weight: 267.53
• EINECS: 243-271-2
• Product Categories: metal amide complex;ALD Precursors
• Mol File: 19756-04-8.mol

Chemical Properties

• Melting Point: 57-60 °C(lit.)
• Boiling Point: 80°C 0,1mm
• Flash Point: >65℃
• Appearance: /solid
• Storage Temp.: water-free area
• Sensitive: moisture sensitive, store cold
• CAS DataBase Reference: TETRAKIS(DIMETHYLAMINO)ZIRCONIUM(CAS DataBase Reference)
• NIST Chemistry Reference: TETRAKIS(DIMETHYLAMINO)ZIRCONIUM(19756-04-8)
• EPA Substance Registry System: TETRAKIS(DIMETHYLAMINO)ZIRCONIUM(19756-04-8)

Safety Data

• Hazard Codes: F,Xi
• Statements: 11-14/15-36/37/38
• Safety Statements: 16-26-36-43
• RIDADR: UN 3396 4.3/PG 2
• WGK Germany: 3
• TSCA: No
• Hazardous Substances Data: 19756-04-8(Hazardous Substances Data)

Usage

Uses

Used in Deposition Systems:
TETRAKIS(DIMETHYLAMINO)ZIRCONIUM is used as a precursor for atomic layer deposition of zirconium. This process is essential for creating thin films of zirconium with precise control over the thickness and uniformity, which is crucial in various applications.
Used in Gas Sensor Industry:
TETRAKIS(DIMETHYLAMINO)ZIRCONIUM is used as a precursor for the development of gas sensors. The deposited zirconium layers can be integrated into the sensor design to enhance their sensitivity and selectivity towards specific gases.
Used in Microelectronics Industry:
In the microelectronics industry, TETRAKIS(DIMETHYLAMINO)ZIRCONIUM is used as a precursor for the fabrication of high-k dielectrics. These dielectric materials are vital for improving the performance of transistors and other microelectronic components by providing better insulation and reducing power consumption.

InChI:InChI=1/4C2H6N.Zr/c4*1-3-2;/h4*1-2H3;/q4*-1;+4/rC8H24N4Zr/c1-9(2)13(10(3)4,11(5)6)12(7)8/h1-8H3

Upstream product

• 3585-33-9 lithium dimethylamide 
• 216780-49-3 Zr(NMe₂)3(Si(SiMe₃)3) 
• 7732-18-5 water 
• 10026-11-6 zirconium(IV) chloride 
• 124-40-3 dimethyl amine 
• 1030839-76-9 [Zr(κ3-N,N,N-tris(4,4-dimethyl-2-oxazolinyl)phenylborate)Cl3] 

Downstream Products

• 7440-67-7 zirconium(IV) oxide 
• 192136-54-2 Zr(N(CH₃)2)3(OC₄H₈)2⁽¹⁺⁾*B(C₆H₅)4^(1-)=[Zr(N(CH₃)2)3(OC₄H₈)2]B(C₆H₅)4 
• 473699-47-7 [Zr(N(CH₃)2)2(C₁₀H₆(NC₆H₅)C₉H₆N)2] 
• 697741-34-7 [Zr(C₁₀H₆(N(benzyl))C₉H₆N)(NMe₂)3] 
• 697741-40-5 [Zr(C₁₀H₆(N(3,5-Me₂Ph))C₉H₆N)2(NMe₂)2] 
• 1449697-17-9 C₂₅H₂₃F₁₀N₅Zr 
• 64389-72-6 neopentylzirconium tris(dimethylamide) 
• 203790-69-6 (((CH₃)2C₆H₃NC₂H₄)2O)Zr(N(CH₃)2)2 
• 203790-68-5 (((CH(CH₃)2)2C₆H₃NC₂H₄)2O)Zr(N(CH₃)2)2 
• 224637-89-2 [(Me₂N)3Zr(SiBu(t)Ph₂)2]^(1-) 
• 688739-39-1 [Zr(NMe₂)5]^(1-) 
• 94768-38-4 Zr(OC₆H₂(C(CH₃)3)3)2(N(CH₃)2)2 
• 263547-56-4 (((CH₃)2CH)2C₆H₃NCH)2C₄H₂NZr(N(CH₃)2)3 

Relevant articles and documents

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.

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

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.

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.

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.

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.

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

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.

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

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.