Reaction of stannenes and phosphastannenes with aldehydes and ketones: New tin four-membered ring derivatives

Rodi, A. Kandri; Anselme, G.; Ranaivonjatovo, H.; Escudié, J.

doi:10.1007/bf02252165

Cited by 4 publications

(4 citation statements)

References 29 publications

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“…Spectroscopic evidence for reversible retro-cycloaddition was obtained after consecutive heating and cooling of the C 6 D 6 solutions of 3 and 4 . Similar reactivity is known for compounds with genuine Ge–P and Sn–P double bonds . The mechanism for the formation of 3 and 4 was confirmed as concerted [2+2] cycloaddition by quantum chemical calculations using model compounds…”

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confidence: 63%

N-Heterocyclic Carbene-Stabilized Germanium and Tin Analogues of Heavier Nitriles: Synthesis, Reactivity, and Catalytic Application

et al. 2019

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The synthesis of stable heavier analogues of nitriles as monomeric tetrylene−phosphinidenes Mes TerEP(IDipp) (E = Ge, Sn; Mes Ter = 2,6-Mes 2 C 6 H 3 , IDipp = C([N-(2,6-iPr 2 C 6 H 4 )CH] 2 ) was achieved by taking advantage of NHC (N-heterocyclic carbene, here IDipp) coordination to the low-valent phosphorus center. Multiple bonding character of the E−P bonds was examined experimentally and computationally. Both germanium and tin compounds undergo [2+2] cycloaddition with diphenylketene, whereas reaction of the tin derivative with tris(pentafluorophenyl)borane provided unique "push−pull" phosphastannene ( Mes Ter)(Ar)Sn = P(IDipp) (Ar = C 6 F 4 [B(F)(C 6 F 5 ) 2 ]). Going further, we demonstrated the potential of tetrylene−phosphinidene complexes in catalytic hydroboration of carbonyl compounds.

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confidence: 63%

N-Heterocyclic Carbene-Stabilized Germanium and Tin Analogues of Heavier Nitriles: Synthesis, Reactivity, and Catalytic Application

et al. 2019

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“…The key quantity will be the stability of Me 2 SnO about which little seems to be known. Provided the SnO double bond − is as strong or stronger than D (OSO) and likewise D (NNO), then these reactions are feasible. The values for D (OSO) and D (NNO) are easily calculated from well-established thermochemistry at 552 and 167 kJ mol -1 .…”

Section: Discussionmentioning

confidence: 99%

“…Theoretical calculations 49 suggest that species such as dimethylstannanone, with double bonds between oxygen and tin, are not likely to exist. Despite this a stannanone has been implicated in stannaoxetane decomposition …”

Section: Referencesmentioning

confidence: 99%

First Gas-Phase Detection of Dimethylstannylene and Time-Resolved Study of Some of Its Reactions

et al. 2002

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Using a laser flash photolysis/laser probe technique, we report the observation of strong absorption signals in the wavelength region 450-520 nm (highest intensity at 514.5 nm) from four potential precursors of dimethylstannylene, SnMe(2), subjected to 193 nm UV pulses. From GC analyses of the gaseous products, combined with quantum chemical excited state CIS and TD calculations, we can attribute these absorptions largely to SnMe(2), with SnMe(4) as the cleanest source of the species. Kinetic studies have been carried out by time-resolved monitoring of SnMe(2). Rate constants have been measured for its reactions with 1,3-C(4)H(6), MeC[triple bond]CMe, MeOH, 1-C(4)H(9)Br, HCl, and SO(2). No evidence could be found for reaction of SnMe(2) with C(2)H(4), C(3)H(8), Me(3)SiH, GeH(4), Me(2)GeH(2), or N(2)O. Limits of less than 10(-13) cm(3) molecule(-1) s(-1) were set for the rate constants for these latter reactions. These measurements showed that SnMe(2) does not insert readily into C-H, Si-H, Ge-H, C-C, Si-C, or Ge-C bonds. It is also unreactive with alkenes although not with dienes or alkynes. It is selectively reactive with lone pair donor molecules. The possible mechanisms of these reactions are discussed. These results represent the first visible absorption spectrum and rate constants for any organo-stannylene in the gas phase.

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“…[3][4][5][6] The chemistry of the Sn=C bond has been sparsely explored. Only punctual studies of the reactions of long-lived stannenes with protic reagents, [3,7,8] benzophenone, [14] 2,3-dimethylbutadiene, [8] methyl iodide, [7b] reduction by LiAlH 4 [7b] along with their head-to-tail dimerization have been reported. [7] Investigation of the chemical behaviour of the transient stannene Me 2 Sn=C(SiMe 3 ) 2 [15] has been limited to its reaction with alkenes, dienes, azides and phenyllithium.…”

Section: Introductionmentioning

confidence: 99%

A Nearly Planar Stannene with a Reactive Tin–Carbon Double Bond

et al. 2008

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Bis(2,4,6‐triisopropylphenyl)‐2,7‐di‐tert‐butylfluorenylidenestannane, Tip2Sn=CR2, an isolable stannene that displays a deep‐purple colour, was synthesized by dehydrofluorination of the corresponding fluorostannane by tert‐butyllithium. It exhibits the shortest Sn=C distance [2.003(5) Å] and the slightest twisting around this unsaturation (10°) among the known stannenes. Its reaction with benzaldehyde according to a [2+2] cycloaddition and that with α‐ethylenic aldehydes and ketones such as crotonaldehyde and methyl vinyl ketone by a [2+4] cycloaddition proceeded in near‐quantitative yield. With acetone, an ene reaction occurred. The four‐membered ring 1,2‐oxastannacyclobutane obtained with benzaldehyde underwent a ring expansion with a second molecule of benzaldehyde to afford the six‐membered ring dioxastannacyclohexane.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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Reaction of stannenes and phosphastannenes with aldehydes and ketones: New tin four-membered ring derivatives

Cited by 4 publications

References 29 publications

N-Heterocyclic Carbene-Stabilized Germanium and Tin Analogues of Heavier Nitriles: Synthesis, Reactivity, and Catalytic Application

N-Heterocyclic Carbene-Stabilized Germanium and Tin Analogues of Heavier Nitriles: Synthesis, Reactivity, and Catalytic Application

First Gas-Phase Detection of Dimethylstannylene and Time-Resolved Study of Some of Its Reactions

A Nearly Planar Stannene with a Reactive Tin–Carbon Double Bond

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