Reactions of d0 alkylidene and amide complexes with silanes

Diminnie, Jonathan B.; Liu, Xiaozhan; Cai, Hu; Wu, Zhongzhi; Blanton, Jaime R.; Chen, Tianniu; Tuinman, Albert A.; Quisenberry, Keith T.; Vallet, C. E.; Zuhr, R.A.; Beach, David B.; Peng, Zhihui; Wu, Yong; Concolino, Thomas E.; Rheingold, Arnold L.; Chen, Xue-Tai

doi:10.1351/pac200173020331

Cited by 10 publications

(2 citation statements)

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“…We have studied how H−Si bonds in silanes react with the π bonds in the MCHR and with the d−p π bonds in the M−NR 2 moieties and mechanisms in these reactions. In the former, we chose the Cp-free d 0 high-oxidation-state alkylidene complexes (RCH 2 )Ta(PMe 3 ) 2 (CHR‘) 2 , containing phosphine ligands, in the hope that such ligands would help stabilize the resulting reaction products. , In the latter, Cp-free d 0 high-oxidation-state amide complexes M(NMe 2 ) n (M = Ti, Zr, Hf, Ta) were used. − The reactions of metal amides with silanes have also played an important role in the formation of M−Si−N ternary films as diffusion barrier materials in very-large-scale-integrated microelectronic devices, as discussed below.…”

Section: Reactions Of Silanes With Alkylidene and Amide Complexesmentioning

confidence: 99%

“…Kinetic studies of the reactions of 37 with H 2 SiMePh and D 2 SiMePh at 10 °C show that a dissociative mechanism is operative in this reaction. , This pathway involves the loss of a PMe 3 ligand to open a coordination site on the Ta center, followed by rate-determining addition of the silane to the TaC bond to give 39 (Scheme ). For example, a steady-state approximation gives eqs 15 and 16 44b…”

Section: Reactions Of Silanes With Alkylidene and Amide Complexesmentioning

confidence: 99%

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Transition-Metal Silyl Complexes and Chemistry in the Reactions of Silanes with Transition-Metal Complexes

Morton

Chen

2004

Organometallics

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Studies from the authors' group of early-transition-metal silyl complexes and pathways in the reactions of silanes with transition-metal complexes are reviewed. Cyclopentadienyl-free, group 4 alkyl silyl, group 5 alkylidene silyl, group 6 alkylidyne silyl, and groups 4 and 5 amide and imide silyl complexes have been prepared and characterized. In the reactions of silanes with alkylidene and amide complexes, the MCH− π bonds and d−p π bonds in MNR2 were found to attack Si in silanes. The mechanistic studies here help in understanding the formation of mixtures of TiN and Si3N4 from the reactions of Ti(NMe2)4 and SiH4 as microelectronic diffusion barrier materials.

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Section: Reactions Of Silanes With Alkylidene and Amide Complexesmentioning

confidence: 99%

Section: Reactions Of Silanes With Alkylidene and Amide Complexesmentioning

confidence: 99%

Transition-Metal Silyl Complexes and Chemistry in the Reactions of Silanes with Transition-Metal Complexes

Morton

Chen

2004

Organometallics

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ChemInform Abstract: Reactions of D0 Alkylidene and Amide Complexes with Silanes

et al. 2001

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organic chemistry, review organic chemistry, review Z 0200 42 -294 Reactions of D0 Alkylidene and Amide Complexes with Silanes -[15 refs.]. -(DIMINNIE, JONATHAN B.; LIU, XIAOZHAN; CAI, HU; WU, ZHONGZHI; BLANTON, JAIME R.; CHEN, TIANNIU; TUINMAN, ALBERT A.; QUISENBERRY, KEITH T.; VALLET, CATHERINE E.; ZUHR, RAY A.; ET AL.; Pure Appl. Chem. 73 (2001) 2, 331-335; Dep. Chem., Univ. Tenn., Knoxville, TN 37996, USA; EN)

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Unusual reaction of a tungsten alkylidyne complex with water. Formation, characterization, and crystal structures of oxo trimers

Dougan

Chen

2011

Sci. China Chem.

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O) 3 ]·2benzene-d 6 (3·2benzene-d 6 ), respectively, each containing two alkyl ligands per W atom. This is in contrast to the dimer W 2 O 2 (-O)(CH 2 CMe 3 ) 6 , containing three alkyl ligands per W atom, from the previously reported reaction of the alkyl alkylidyne analog W(CH 2 CMe 3 ) 3 -(CCMe 3 ) with H 2 O. In the reaction of 1 with D 2 O in THF, an unstable intermediate W 2 O 2 (-O)(CD 2 SiMe 3 ) 2 (CH 2 CMe 3 ) 4 (4-d 4 ) was identified. Kinetic studies of the reactions of 1 with excess H 2 O and D 2 O in THF-d 8 , yielding 4 and 4-d 4 , respectively, give a kinetic isotope effect (KIE) of 3.46(3) at 298(1) K, suggesting that the disappearance of 1 is a rate-determining step. alkylidyne, water, oxo complexes, kinetic isotope effectMany early transition metal complexes are moisturesensitive, and reactions of metal complexes with water have been used to make metal oxides [1][2][3] in, e.g. microelectronic industry. Such reactions with water have attracted much attention [4][5][6][7][8][9][10][11][12][13]. Schrock, Lippard and coworkers reported the formation of the dimer W 2

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Reactions of d0 alkylidene and amide complexes with silanes

Cited by 10 publications

References 3 publications

Transition-Metal Silyl Complexes and Chemistry in the Reactions of Silanes with Transition-Metal Complexes

Transition-Metal Silyl Complexes and Chemistry in the Reactions of Silanes with Transition-Metal Complexes

ChemInform Abstract: Reactions of D0 Alkylidene and Amide Complexes with Silanes

Unusual reaction of a tungsten alkylidyne complex with water. Formation, characterization, and crystal structures of oxo trimers

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