- Organotin compounds containing a bulky (Me3Si)3C or related ligand. Crystal structures of {(Me3Si)3CMe(O2NO)Sn}2O, (PhMe2Si)3CSnMeCl2 and (PhMe2Si)3CSnCl3
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Some compounds having very bulky ligands, mainly (Me3Si)3C (denoted by Tsi) or (PhMe2Si)3C (denoted by Tpsi), attached to functional tin centres have been studied. Treatment of TsiSnR2Cl, R=Me or Ph, with one equivalent of ICl gave the corresponding chloride TsiSnRCl2, and use of an excess of ICl gave TsiSnCl3 in both cases. Reaction of either chloride with one equivalent of Br2 gave the dibromide TsiSnRBr2; when an excess of Br2 was used TsiSnMe2Cl still gave the dibromide but TsiSiPh2Cl gave the tribromide TsiSnBr3. Reaction of TsiSnMe2Br with AgSCN or Ag2O gave TsiSnMe2NCS and (TsiSnMe2)2O, respectively, but when the crude product from the reaction of TsiSnMeBr2 with AgNO3 was recrystallized from MeOH the nitrato-oxide {TsiMe(O2NO)Sn}2O was obtained. In a seemingly previously unreported type of reaction, the alkoxide TsiSnMe2OEt reacted with ICl, Br2, or I2 to give TsiSnMe2X, X=Cl, Br, or I, respectively, and Bu3SnOEt likewise reacted with ICl to give Bu3SnCl. The chlorides TsiSnMe2Cl and TsiSnMeCl2 gave the hydrides TsiSnMe2H and TsiSnMeH2 on treatment with LiAlH4, but in the case of TpsiSnMe2Cl the Tpsi-Sn bond was cleaved to give TpsiH. The compound (Me3Si)2C(SnMe2Ph)(SiMe2Cl) reacted with a 1 M proportion of AgBF4 in CH2Cl2 with cleavage of the Sn-Ph bond to give the difluoride (Me3Si)2C(SnMe2F)(SiMe2F). The crystal structures of the monomeric compounds {TsiMe(O2NO)Sn}2O, TpsiSnMeCl2 and TpsiSnCl3 are reported; {TsiMe(O2NO)Sn}2O provides the first example of unidentate bonding of an NO3 group to four-coordinate tin.
- Al-Juaid, Salih S.,Al-Rawi, Mustafa,Eaborn, Colin,Hitchcock, Peter B.,Smith, J. David
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p. 215 - 226
(2007/10/03)
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- Synthesis and properties of some crowded organotin compounds
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The preparations of the compounds (Me3Si)3CSnMe2X (X= Cl, Br, I, CN, NCS, O2CMe, O2CCF3, O3SMe, or NO3), (Me3Si)3CSnPh2X (X= Cl or Br), and (Me2PhSi)3CSnMe2X (X= Me, Cl, Br or I) are described.Treatment of (Me2PhSi)3CSnMe2Cl with one equivalent of MeLi gives (Me2PhSi)3CSnMe3, but with additional MeLi (Me2PhSi)3CLi is formed.The compound (Me3Si)2C(SnMe3)2 is obtained by reaction of (Me3Si)2CCl2 with either one or two equivalents of Me3SnLi, and on treatment with MeLi gives the useful reagent (Me3Si)2(Me3Sn)CLi.The latter reacts with Me2SiCl2 and give (Me3Si)2(Me3Sn)C(SiMe2Cl) and with Me2SiHCl to give (Me3Si)2(Me3Sn)C(SiMe2H), which reacts with a one molar proportion of Br2 to give (Me3Si)2(Me3Sn)C(SiMe2Br), and with a two molar proportion of Br2 to give (Me3Si)2C(SnMe2Br)(SiMe2Br).Reaction of (Me3Si)2C(SnMe3)2 with two equivalents of ICl or Br2 gives the dihalides (Me3Si)2C(SnMe2X)2 (X= Cl or Br), and reaction of (Me3Si)2C(SnMe2Br)(SiMe2Br) with PhLi gives (Me3Si)2C(SnMe2Ph)(SiMe2Br).
- Dhaher, Saadi M.,Eaborn, Colin,Smith, J. David
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- PREPARARTION AND CRYSTAL STRUCTURES OF THE CROWDED ORGANOTIN FLUORIDES (PhMe2Si)3CSnMe2F, (Me3Si)3CSnMe2F, AND (Me3Si)3CSnPh2F
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X-Ray diffraction studies have established that crystals of the organotin fluorides (Me3Si)3CSnMe2F, (Me3Si)3CSnPh2F, and (PhMe2Si)3CSnMe2F are made up of discrete molecules with no intermolecular F...Sn interactions.The data for (PhMe2Si)3CSnMe2F are of good quality (R=0.029, R'=0.040), and provide the first measurement of an Sn-F bond length (1.965(2) Angstroem) in a four-coordinate tin species.
- Al-Juaid, Salih S.,Dhaher, Saadi M.,Eaborn, Colin,Hitchcock, Peter B.,Smith, J. David
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p. 117 - 128
(2007/10/02)
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