Direct transfer of aliphatic and aromatic substituents from organosilatranes to mercury(II) species

J. Dirk Nies; Jon M. Bellama; Nava Ben-Zvi

doi:10.1016/0022-328X(85)80362-4

Direct transfer of aliphatic and aromatic substituents from organosilatranes to mercury(II) species

J. Dirk Nies^*
, Jon M. Bellama
, Nava Ben-Zvi

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

17 Scopus citations

Abstract

The relative reaction rates of several silatranes (derivatives of 2,8.9-trioxa-5-aza- 1-silatricyclo[3.3.3.0^1,5]undecane) and HgCl₂ in acetone-d₆to yield the corresponding organomercury compound are of the order of e.g., 5 × 10^-1 1 mol^-1 sec^-1 or slightly less, a rate that is unexpectedly high compared to the essentially inert parent organotrialkoxysilanes. Thus, the apical Si&.zsbnd;C bond of the silatrane is extraordinarily susceptible to direct electrophilic attack by mercury(II). The rates decrease in the order CH₂CH, C₆H₅, p-ClC₆H₄ > CH₃ > CH₃CH₂, CH₃CH₂CH₂ > C₆H₁₁, ClCH₂, Cl₂CH, CH₃CH₂O. The effects of varying the solvent and the counterions are noted, and the probable mechanism is discussed.

Original language	English
Pages (from-to)	315-319
Number of pages	5
Journal	Journal of Organometallic Chemistry
Volume	296
Issue number	3
DOIs	https://doi.org/10.1016/0022-328X(85)80362-4
State	Published - 3 Dec 1985
Externally published	Yes

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10.1016/0022-328X(85)80362-4

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@article{e1ff9aed5c2f4fe988a45558ab6248dd,

title = "Direct transfer of aliphatic and aromatic substituents from organosilatranes to mercury(II) species",

abstract = "The relative reaction rates of several silatranes (derivatives of 2,8.9-trioxa-5-aza- 1-silatricyclo[3.3.3.01,5]undecane) and HgCl2 in acetone-d6to yield the corresponding organomercury compound are of the order of e.g., 5 × 10-1 1 mol-1 sec-1 or slightly less, a rate that is unexpectedly high compared to the essentially inert parent organotrialkoxysilanes. Thus, the apical Si\&.zsbnd;C bond of the silatrane is extraordinarily susceptible to direct electrophilic attack by mercury(II). The rates decrease in the order CH2CH, C6H5, p-ClC6H4 > CH3 > CH3CH2, CH3CH2CH2 > C6H11, ClCH2, Cl2CH, CH3CH2O. The effects of varying the solvent and the counterions are noted, and the probable mechanism is discussed.",

author = "Nies, \{J. Dirk\} and Bellama, \{Jon M.\} and Nava Ben-Zvi",

year = "1985",

month = dec,

day = "3",

doi = "10.1016/0022-328X(85)80362-4",

language = "אנגלית",

volume = "296",

pages = "315--319",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

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}

TY - JOUR

T1 - Direct transfer of aliphatic and aromatic substituents from organosilatranes to mercury(II) species

AU - Nies, J. Dirk

AU - Bellama, Jon M.

AU - Ben-Zvi, Nava

PY - 1985/12/3

Y1 - 1985/12/3

N2 - The relative reaction rates of several silatranes (derivatives of 2,8.9-trioxa-5-aza- 1-silatricyclo[3.3.3.01,5]undecane) and HgCl2 in acetone-d6to yield the corresponding organomercury compound are of the order of e.g., 5 × 10-1 1 mol-1 sec-1 or slightly less, a rate that is unexpectedly high compared to the essentially inert parent organotrialkoxysilanes. Thus, the apical Si&.zsbnd;C bond of the silatrane is extraordinarily susceptible to direct electrophilic attack by mercury(II). The rates decrease in the order CH2CH, C6H5, p-ClC6H4 > CH3 > CH3CH2, CH3CH2CH2 > C6H11, ClCH2, Cl2CH, CH3CH2O. The effects of varying the solvent and the counterions are noted, and the probable mechanism is discussed.

AB - The relative reaction rates of several silatranes (derivatives of 2,8.9-trioxa-5-aza- 1-silatricyclo[3.3.3.01,5]undecane) and HgCl2 in acetone-d6to yield the corresponding organomercury compound are of the order of e.g., 5 × 10-1 1 mol-1 sec-1 or slightly less, a rate that is unexpectedly high compared to the essentially inert parent organotrialkoxysilanes. Thus, the apical Si&.zsbnd;C bond of the silatrane is extraordinarily susceptible to direct electrophilic attack by mercury(II). The rates decrease in the order CH2CH, C6H5, p-ClC6H4 > CH3 > CH3CH2, CH3CH2CH2 > C6H11, ClCH2, Cl2CH, CH3CH2O. The effects of varying the solvent and the counterions are noted, and the probable mechanism is discussed.

UR - https://www.scopus.com/pages/publications/0001146911

U2 - 10.1016/0022-328X(85)80362-4

DO - 10.1016/0022-328X(85)80362-4

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AN - SCOPUS:0001146911

SN - 0022-328X

VL - 296

SP - 315

EP - 319

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 3

ER -

Direct transfer of aliphatic and aromatic substituents from organosilatranes to mercury(II) species

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