468 research outputs found
Unusual Anions [LAl(SH)(S)]<sup>-</sup> and [LAl(S)<sub>2</sub>]<sup>2-</sup> Stabilized by Weakly Coordinating Imidazolium Cations. Synthesis of LAl(SSiMe<sub>2</sub>)<sub>2</sub>O (L = HC[C(Me)N(Ar)]<sub>2</sub>, Ar = 2,6-<i>i</i>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)
Deprotonation of an Al−SH moiety has been achieved easily by
using N-heterocyclic carbene as the base. Monomeric mono- and
bis-imidazolium salts [CtH+][LAl(SH)(S)]- ([CtH+] = N,N‘-bis-tert-butylimidazolium), [CmH+][LAl(SH)(S)]-, and [CmH+]2[LAl(S)2]2-
([CmH+] = N,N‘-bismesitylimidazolium), containing unusual anions
[LAl(SH)(S)]- and [LAl(S)2]2-, have been synthesized in nearly
quantitative yields. Furthermore, [CmH+]2[LAl(S)2]2- has been
successfully used for the preparation of LAl(SSiMe2)2O containing
the [O(Me2SiS)2]2- ligand
Unusual Anions [LAl(SH)(S)]<sup>-</sup> and [LAl(S)<sub>2</sub>]<sup>2-</sup> Stabilized by Weakly Coordinating Imidazolium Cations. Synthesis of LAl(SSiMe<sub>2</sub>)<sub>2</sub>O (L = HC[C(Me)N(Ar)]<sub>2</sub>, Ar = 2,6-<i>i</i>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)
Deprotonation of an Al−SH moiety has been achieved easily by
using N-heterocyclic carbene as the base. Monomeric mono- and
bis-imidazolium salts [CtH+][LAl(SH)(S)]- ([CtH+] = N,N‘-bis-tert-butylimidazolium), [CmH+][LAl(SH)(S)]-, and [CmH+]2[LAl(S)2]2-
([CmH+] = N,N‘-bismesitylimidazolium), containing unusual anions
[LAl(SH)(S)]- and [LAl(S)2]2-, have been synthesized in nearly
quantitative yields. Furthermore, [CmH+]2[LAl(S)2]2- has been
successfully used for the preparation of LAl(SSiMe2)2O containing
the [O(Me2SiS)2]2- ligand
Unusual Anions [LAl(SH)(S)]<sup>-</sup> and [LAl(S)<sub>2</sub>]<sup>2-</sup> Stabilized by Weakly Coordinating Imidazolium Cations. Synthesis of LAl(SSiMe<sub>2</sub>)<sub>2</sub>O (L = HC[C(Me)N(Ar)]<sub>2</sub>, Ar = 2,6-<i>i</i>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)
Deprotonation of an Al−SH moiety has been achieved easily by
using N-heterocyclic carbene as the base. Monomeric mono- and
bis-imidazolium salts [CtH+][LAl(SH)(S)]- ([CtH+] = N,N‘-bis-tert-butylimidazolium), [CmH+][LAl(SH)(S)]-, and [CmH+]2[LAl(S)2]2-
([CmH+] = N,N‘-bismesitylimidazolium), containing unusual anions
[LAl(SH)(S)]- and [LAl(S)2]2-, have been synthesized in nearly
quantitative yields. Furthermore, [CmH+]2[LAl(S)2]2- has been
successfully used for the preparation of LAl(SSiMe2)2O containing
the [O(Me2SiS)2]2- ligand
Unusual Anions [LAl(SH)(S)]<sup>-</sup> and [LAl(S)<sub>2</sub>]<sup>2-</sup> Stabilized by Weakly Coordinating Imidazolium Cations. Synthesis of LAl(SSiMe<sub>2</sub>)<sub>2</sub>O (L = HC[C(Me)N(Ar)]<sub>2</sub>, Ar = 2,6-<i>i</i>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)
Deprotonation of an Al−SH moiety has been achieved easily by
using N-heterocyclic carbene as the base. Monomeric mono- and
bis-imidazolium salts [CtH+][LAl(SH)(S)]- ([CtH+] = N,N‘-bis-tert-butylimidazolium), [CmH+][LAl(SH)(S)]-, and [CmH+]2[LAl(S)2]2-
([CmH+] = N,N‘-bismesitylimidazolium), containing unusual anions
[LAl(SH)(S)]- and [LAl(S)2]2-, have been synthesized in nearly
quantitative yields. Furthermore, [CmH+]2[LAl(S)2]2- has been
successfully used for the preparation of LAl(SSiMe2)2O containing
the [O(Me2SiS)2]2- ligand
Synthesis and Structural Characterization of P-Functionalized Metallacyclophosphazenes<sup>†</sup>
A facile, high-yield synthesis of
Cl3VNSiMe3 (1) is reported.
1 and the metal nitride halides Cl3MoN
and Cl3WN react with
[{(Me2N)2PNH2}2N]+Cl-
to form the six-membered metallacyclophosphazenes
[(Me2N)2PN]2VCl2
(2),
[(Me2N)2PN]2MoCl3·MeCN
(3), and
[(Me2N)2PN]2WCl3·MeCN
(4), respectively. The X-ray structure
determinations of 2 and 3 show the compounds to
have planar six-membered rings of distorted geometry
Hydrolytic Synthesis of an Alumoxane Hydride Bearing Terminal Pyrazolato Ligands<sup>†</sup>
The novel alumoxane hydride [(μ-η1:η1-3,5-tBu2pz)2(η1-3,5-tBu2pz)2(μ3-O)(μ-Al)3H3]·2THF (2; 3,5-tBu2pz = 3,5-tert-butylpyrazolato) is formed when aluminum dihydride [(μ-η1:η1-3,5-tBu2pz)(μ-Al)H2]2 (1) is
reacted with 1 equiv of water. The core of compound 2
consists of two tetra- and one hexacoordinated Al atoms
with short Al−O bonds. The two central N2Al2O ring
systems share a common Al−O edge with a hexacoordinated Al atom, and two of the pyrazolato ligands bind
in an η1 and μ-η1:η1 arrangement
Hydrostannylation of Ketones and Alkynes with LSnH [L = HC(CMeNAr)<sub>2</sub>, Ar = 2,6-<i>i</i>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>]
The reactions of the stable β-diketiminate tin(II) hydride LSnH [L = HC(CMeNAr)2, Ar = 2,6-iPr2C6H3] with different ketones (Ph2CO, 2-Py2CO, cyPr2CO, and 2-C4H3SCOCF3) generated a variety of tin(II) alkoxides (1−4) in high yield. The activated terminal alkynes (HCCCO2R, R = Me, Et) react with LSnH to yield the tin(II) substituted terminal alkenes (5−6) instead of dihydrogen elimination although the Sn−H and C−H bonds are differently polarized. Furthermore, LSnH reacts with disubstituted alkyne (RO2CCCCO2R, R = Et, tBu) in toluene at room temperature to form the stannylene substituted internal alkenes (7−8). Compounds 1−8 were characterized by microanalysis and multinuclear NMR spectroscopy. Moreover compounds 3, 4, 5, and 7 were characterized by X-ray crystallography, and the resulting structures confirmed the monomeric nature, in which the tin centers reside in a trigonal-pyramidal environment
Oxidative Addition of Ammonia at a Silicon(II) Center and an Unprecedented Hydrogenation Reaction of Compounds with Low-Valent Group 14 Elements Using Ammonia Borane
Oxidative Addition of Ammonia at a Silicon(II) Center and an Unprecedented Hydrogenation Reaction of Compounds with Low-Valent Group 14 Elements Using Ammonia Boran
Synthesis and Structure of a S<sub>4</sub>Si<sub>4</sub> Cage Compound<sup>†</sup>
The reaction of the tetraaminodisilane R2Si2(NH2)4 (R = CH(SiMe3)2) with liquid H2S at −70 °C
resulted in the formation of a R4S4Si4 cage. The core of
the molecule consists of four five-membered rings. Two
disilane units are bridged cross over by four sulfur
atoms. This is a new structural type in the group of
silicon−sulfur ring and cluster compounds
Stannasiloxanes with Acyclic, Bicyclic, and Cubic Core Structures:  X-ray Crystal Structure of the Bicyclic Compound [RSi(OSnPh<sub>2</sub>O)<sub>3</sub>SiR] (R = (2,6-Me<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)NSiMe<sub>3</sub>)<sup>†</sup>
The reactions of the (arylamino)silanetriols with mono-, di-,
and trifunctional alkyl/aryl
tin(IV) chlorides have been investigated. Treatment of
(arylamino)silanetriols RSi(OH)3
(1,
2) with Me3SnCl leads to the isolation of
the acyclic stannasiloxanes RSi(OSnMe3)3
(R =
(2,6-Me2C6H3)NSiMe3
(3),
(2,6-i-Pr2C6H3)NSiMe3
(4)), which are potential precursors for the
preparation of metallasiloxanes. The reactions between the
silanetriols 1 and 2 and
R‘2SnCl2 in a 2:3 molar ratio yield the bicylic stannasiloxanes
[RSi(OSnR‘2O)3SiR] (R =
(2,6-Me2C6H3)NSiMe3, R‘
= Me (5); R =
(2,6-Me2C6H3)NSiMe3,
R‘ = Ph (6); R = (2,6-i-Pr2C6H3)NSiMe3, R‘
= Me (7); R =
(2,6-i-Pr2C6H3)NSiMe3,
R‘ = Ph (8)). The cubic
stannasiloxanes [RSiO3SnPh]4 (R =
(2,6-Me2C6H3)NSiMe3
(9);
(2,6-i-Pr2C6H3)NSiMe3
(10))
are easily prepared in good yields by starting from the respective
silanetriols and PhSnCl3.
In all the reactions NEt3 is used as the hydrogen
chloride acceptor. The new stannasiloxanes
3−10 have been extensively characterized by
means of their analytical data and mass, IR,
and NMR (1H, 29Si and
119Sn) spectral data. The solid-state structure
of the bicyclic compound
6 has been determined by X-ray diffraction studies
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