“…[4] The most commonly used reagent of this class of compounds is tributyltin hydride, which is widely used as a reducing agent in organic and inorganic chemistry. [5] To our knowledge, there are no hydrostannylation reactions described using tin(II) hydride. Herein, we report the first hydrostannylation reactions of carbon dioxide, ketones, aldehydes, alkynes, and carbodiimides with [LSnH] (2, L= HC{CMeN(2,6-iPr 2 C 6 H 3 )} 2 ).…”
If anything can, tin can: The tin(II) hydride species [LSnH] (L=HC{CMeN(2,6‐iPr2C6H3)}2) reacts with various compounds containing unsaturated CO, CC, or CN bonds, which results in simultaneous transfer of hydrogen and {LSn} to the organic substrates and elegantly generates new tin(II) compounds. These unique stannylene compounds incorporate a lone pair of electrons that is suitable for complexation with transition‐metal species.
“…[4] The most commonly used reagent of this class of compounds is tributyltin hydride, which is widely used as a reducing agent in organic and inorganic chemistry. [5] To our knowledge, there are no hydrostannylation reactions described using tin(II) hydride. Herein, we report the first hydrostannylation reactions of carbon dioxide, ketones, aldehydes, alkynes, and carbodiimides with [LSnH] (2, L= HC{CMeN(2,6-iPr 2 C 6 H 3 )} 2 ).…”
If anything can, tin can: The tin(II) hydride species [LSnH] (L=HC{CMeN(2,6‐iPr2C6H3)}2) reacts with various compounds containing unsaturated CO, CC, or CN bonds, which results in simultaneous transfer of hydrogen and {LSn} to the organic substrates and elegantly generates new tin(II) compounds. These unique stannylene compounds incorporate a lone pair of electrons that is suitable for complexation with transition‐metal species.
“…Reduction of ZrCl 4 with HSnBu 3 resulted in the formation of a brown solid, 1 . Although we have not been able to characterize brown solid 1 structurally, we have found that it is a good starting material for the preparation of zirconium cluster compounds. − Reaction of brown solid 1 with a phosphonium or ammonium chloride provides a direct method for synthesis of compounds containing [Zr 6 Cl 18 H 5 ] 3- cluster anions, as shown in Scheme . 1 ORTEP diagram of [Zr 6 Cl 18 H 5 ] 3- in [Ph 4 P] 3 [Zr 6 Cl 18 H 5 ]·3CH 2 Cl 2 showing 30% probability thermal ellipsoids.…”
Section: Resultsmentioning
confidence: 99%
“…Metrical Parameters of the [Zr 6 Cl 18 H 5 ] 3 - Cluster. Table summarizes the bond distances and angles for compounds 2a ·3CH 2 Cl 2 , 2a ·4C 6 H 5 CH 3 , 2a , 2b , 2c ·2.43CH 3 CN, and 3 ·3CH 2 Cl 2 ·C 6 H 5 CH 3 , as well as [Zr 6 Cl 14 (PR 3 ) 4 H 4 ] (R = Me, Et, or Pr) . As in [Zr 6 Cl 14 (PR 3 ) 4 H 4 ], one of the most outstanding structural features of the compounds containing [Zr 6 Cl 18 H 5 ] 3- cluster anions is that the cluster hydrogen atoms are distributed, probably due to rapid movement of the hydrogen atoms, over eight triangular faces of the octahedron.…”
Section: Discussionmentioning
confidence: 99%
“…The question that immediately arises is, Where are they? The same question arises concerning the [Zr 6 Cl 14 H 4 (PR 3 ) 4 ] molecules 11 and the [Zr 6 Cl 18 H 4 ] 4- ions . X-ray data alone cannot answer this question, but they can help when taken in the context of an analysis as to where the hydrogen atoms might be.…”
Section: Discussionmentioning
confidence: 99%
“…By reducing ZrX 4 (X = Cl, Br) with HSnBu 3 , we have developed a new method to prepare zirconium cluster compounds containing cluster hydrogen atoms under mild reaction conditions (room temperature in organic solvents). − The reduction of ZrCl 4 with HSnBu 3 followed by addition of phosphines yielded pentanuclear cluster compounds [Zr 5 Cl 12 (PR 3 ) 5 H 4 ] and three types of hexanuclear cluster species, principally [Zr 6 Cl 14 (PR 3 ) 4 H 4 ] and [Zr 6 Cl 18 H 5 ] 3- , but also small amounts of [Zr 6 Cl 18 H 4 ] 4- …”
Reduction of ZrCl4 with HSnBu3 followed by
addition of [R4A]Cl resulted in the formation of
[R4A]3[Zr6Cl18H5]
(2a, R = Ph, A = P; 2b, R =
n-Pr, A = N; 2c, R = Et, A = N). Six
zirconium atoms are arranged as an
octahedron with one Cl atom terminally coordinated to each Zr atom and
the other 12 Cl atoms edge-bridging the
octahedron. When [Ph4P]I was used, the compound
[Ph4P]3[Zr6Cl18
-
x
I
x
H5]
(x = 0.81) (3) was isolated.
In
compound 3, I atoms occupy only the terminal positions.
The number of cluster hydrogen atoms in compounds
2a−c and 3 was established by
1H NMR. The X-ray results are consistent with the five
cluster hydrogen atoms
being distributed at or slightly outside the centers of all eight
triangular faces of the octahedron. Compounds
2a−c and 3 were characterized by
X-ray single-crystal diffraction. Compound
2a·3CH2Cl2 crystallized
in the
triclinic space group P1̄ with cell dimensions (20
°C) of a = 15.993(3) Å, b =
22.237(3) Å, c = 14.670(4) Å,
α = 95.31(1)°, β = 112.07(2)°, γ =
82.06(2)°, V = 4784(2) Å3, and
Z = 2. Compound 2a crystallized in
the
tetragonal space group I41/a with
cell dimensions (20 °C) of a = 33.196(2) Å,
b = 33.196(2) Å, c =
15.236(2)
Å, V = 16790(3) Å3, and Z
= 8. Compound
2a·4C6H5CH3
crystallized in the triclinic space group P1̄ with
cell
dimensions (−60 °C) of a = 14.501(5) Å,
b = 26.630(9) Å, c = 14.049(5) Å,
α = 90.39(3)°, β = 94.19(3)°, γ
= 82.59(1)°, V = 5365(3) Å3,
and Z = 2. Compound 2b crystallized in the
cubic space group Im3̄m with
cell
dimensions (−60 °C) of a = 15.039(3) Å,
b = 15.039(3) Å, c = 15.039(3) Å,
V = 3438(1) Å3, and Z =
2.
Compound 2c·2.43MeCN crystallized in the orthorhombic
space group Pnma with cell dimensions (−100 °C)
of
a = 21.156(1) Å, b = 24.584(3) Å,
c = 11.713(2) Å, V = 6092(1)
Å3, and Z = 4. Compound
3·3CH2Cl2·C6H5CH3 crystallized in the monoclinic space group
P21/c with cell dimensions (20 °C)
of a = 19.786(5) Å, b =
19.071(4) Å, c = 27.397(5) Å, β =
90.22(3)°, V = 10337(4) Å3, and
Z = 4.
Nützliches Zinn: Das Zinn(II)‐hydrid [LSnH] (L=HC{CMeN(2,6‐iPr2C6H3)}2) reagiert mit einer Vielzahl an Verbindungen, die ungesättigte C‐O‐, C‐C‐ oder C‐N‐Bindungen enthalten, unter gleichzeitiger Übertragung von Wasserstoff und {LSn} auf das organische Substrat – ein eleganter Zugang zu Zinn(II)‐Verbindungen. Diese einzigartigen Stannylene verfügen über ein freies Elektronenpaar, das sich für die Komplexbildung mit Übergangsmetallen eignet.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
