Synthesis, Isolation, and Characterization of 1,1‐DiGrignard and 1,1‐Dizincio Silanes

Dobrovetsky, Roman; Bravo‐Zhivotovskii, Dmitry; Tumanskii, B. L.; Botoshansky, Mark; Apeloig, Yitzhak

doi:10.1002/ange.201002876

Cited by 5 publications

(6 citation statements)

References 31 publications

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“…The metathesis examples reported during this review period included formation of Si−Ti,Zr,Hf (eq 1) 4 and Si−Zn (eq 2) 5 complexes utilizing potassium salts or utilizing a SilylGrignard reagent (eq 3) 6 or, more rarely, a SilylCalcium reagent (eq 4). 7 Related to these is the reaction that involves a KSiR 3 reagent that displaces a Cp − from Cp 2 Ni to form a new complex with a Ni−Si bond (eq 5).…”

Section: Background and Alternate Synthetic Methods For Si−tm Bond Fo...mentioning

confidence: 99%

“…7 Related to these is the reaction that involves a KSiR 3 reagent that displaces a Cp − from Cp 2 Ni to form a new complex with a Ni−Si bond (eq 5). 8 Neutral ligands may be displaced by a silyl anion, as was the case when (Pz R Me 2 Si) 3 SiK(18-c-6) (pz = pyrazole; R = t Bu, i Pr) was reacted with W(CO) 6 to give (Pz R Me 2 Si) 3 Si−W(CO) 5 K(18-c-6). 9 When 2 equiv of KSi(SiMe 3 ) 3 were reacted with freshly prepared AuI in liquid ammonia, the aurate complex, K[Au{Si-(SiMe 3 ) 3 } 2 ] was the only product detected in solution and isolated in good yields as a toluene solvate.…”

Section: Background and Alternate Synthetic Methods For Si−tm Bond Fo...mentioning

confidence: 99%

“…86 17 The 31 P( 1 H) NMR spectrum at −80 °C shows a single resonance indicating fluxional behavior and potential scrambling of the hydride and silane hydrogens. Deuterium labeling studies (4-17 generated from D 2 SiPh 2 ) confirm scrambling between the three hydrogen atoms of [4][5][6][7][8][9][10][11][12][13][14][15][16][17]. The reaction of (d 30 -SiP Ph 3 )Ru(H)(N 2 ) with D 2 SiPh 2 was also reported.…”

mentioning

confidence: 87%

“…With PhSiH 3 , the substituent produced was a σ-H-SiH 2 Ph, but when the size of the organic substituent of the reacting primary silane is increased from a Ph to a Mes group, only one of the terminal N 2 ligands was lost, leaving one terminal N 2 group in 3-19 still coordinated to Fe. Even a small change of the substituents on the pyridine group from H-to CH 3 -resulted in formation of a dihydride (3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17)(18) instead of the σ-H-SiH 2 Ph product observed in 3-17. With the secondary silane, H 2 SiPh 2 , another variation was observed that involved formation of a σ-H-H in the same position of σ-H-SiH 2 Ph in 3-17.…”

Section: Reactions Of Silanes Initiated By Loss Of a Neutral Ligandmentioning

confidence: 99%

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Reactions of Hydrosilanes with Transition Metal Complexes

2016

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This third review in a series involving reactions of hydrosilanes and transition metal complexes and characterization of the products covers the period 2009 thru 2013. After a brief discussion of other synthetic methods used for the formation of Si-TM complexes, Section 3 provides an extended discussion of the types of ligands and metal complexes used as reactants with hydrosilanes. The increase in use of pincer ligands in forming stable, isolable complexes is featured. Three tables list the complexes reported for primary, secondary, and tertiary silanes. Many reactions leading to SiTM complexes are initiated by loss of a ligand prior to oxidative addition of the hydrosilane or by a metathesis reaction. Structural data are tabulated for the isolated complexes and provide the Si-TM bond ranges for the elements in the "d" block. A major section on nonclassical (σ or agostic) complexes includes two general groupings with Si-H···TM and M-H···Si interactions. A section on solution processes identified by NMR spectroscopy is dominated by hydride exchange examples. A section on bonding outlines a unifying bonding description that has been proposed as well as calculations reported for Si-TM complexes, both real and hypothetical examples.

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Section: Background and Alternate Synthetic Methods For Si−tm Bond Fo...mentioning

confidence: 99%

Section: Background and Alternate Synthetic Methods For Si−tm Bond Fo...mentioning

confidence: 99%

mentioning

confidence: 87%

Section: Reactions Of Silanes Initiated By Loss Of a Neutral Ligandmentioning

confidence: 99%

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Reactions of Hydrosilanes with Transition Metal Complexes

2016

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“…Zugleich ist er Kodirektor des Lise Meitner–Minerva Center. Apeloigs Forschung konzentriert sich auf die Organosiliciumchemie und die Quantenchemie, und in seinen jüngsten Veröffentlichungen in der Angewandten Chemie beschreibt er die Isolierung und Charakterisierung von 1,1‐Dimagnesio‐ und 1,1‐Dizinciosilanen3a und von Silenolaten 3b. Er ist Mitglied des wissenschaftlichen Beirats des Israel Journal of Chemistry…”

Section: Ausgezeichnet …︁unclassified