Kinetic Studies of the Reactions of<scp>Si</scp><scp>C</scp>and<scp>Si</scp><scp>Si</scp>Bonds

Morkin, Tracy L.; Owens, Thomas R.; Leigh, William J.

doi:10.1002/9780470682531.pat0251

Cited by 1 publication

(2 citation statements)

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“…It has long been recognized that the disilenes are able to activate the O-H bond in water and alcohols; in fact, the reaction with water and alcohols is one of the most extensively investigated reactions of disilenes. [6][7][8] Disilene activation of σ-bonds in other important small molecules, such as NH 3 [9][10][11][12][13] 1 and H 2 , [14] has recently been realized. With the ability to selectively give the NH activated product in high yield rather than the coordinated donor adduct, the promise of disilenes in NH activation chemistry is particularly attractive and, to realize the potential, a thorough understanding of the mechanism and stereochemistry of this fundamental reaction is needed.…”

Section: Introductionmentioning

confidence: 99%

“…One of the many exciting developments in this area concerns the chemistry of disilenes, molecules containing a silicon‐silicon double bond. It has long been recognized that the disilenes are able to activate the O‐H bond in water and alcohols; in fact, the reaction with water and alcohols is one of the most extensively investigated reactions of disilenes [6–8] . Disilene activation of σ‐bonds in other important small molecules, such as NH 3 [9–13] 1 and H 2 , [14] has recently been realized.…”

Section: Introductionmentioning

confidence: 99%

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On the Stereochemistry of the NH Bond Activation of Ammonia or Amines by Disilenes: Predictability

Sharif

Özpınar

McOnie

et al. 2023

Chemistry A European J

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The stereochemistry of the addition of NH3 to the stereoisomers of 1,2‐di‐tert‐butyl‐1,2‐bis(2,4,6‐triisopropylphenyl)disilene (Z‐5 or E‐5) is 100 % stereospecific giving two isomeric disilylamines 6 and 7, respectively, derived from syn‐addition to the stereoisomeric disilenes. Variable time normalization analysis studies of the reaction of tetramesityldisilene (3) with isopropylamine (iPrNH2) revealed that the order in both amine and disilene is 1. The kinetic isotope effect for the addition of iPrNH2/iPrND2 to tetramesityldisilene was determined to be 3.04±0.06 at 298 K, a primary KIE, indicating that the proton is transferred in the rate determining step. Competition studies between the addition of PrNH2 and iPrNH2 to tetramesityldisilene resulted in the exclusive formation of the PrNH2 adduct consistent with a nucleophilic addition. Computational studies of the mechanism of the addition of ammonia to E‐5 revealed the lowest energy pathway involves the formation of the donor adduct derived from syn‐addition, followed by intramolecular syn‐transfer of the proton. The formation of the donor adduct is the rate determining step. The results of this study, together with previous studies on the addition of ammonia and amines to disilenes, allow for a refinement of our understanding of the mechanism of this important fundamental reaction in disilene chemistry, and allow us to understand our ability to reliably predict the stereochemical outcomes of future NH σ‐bond activation reactions.

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