Triphenylphosphine oxide adducts of diphenylantimony(V) and diorganotin(IV) Lewis acids: structures of SnPh₂Cl₂·OPPh₃, SnPh₂Cl₂·2OP

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• 作者：Cunningham ; D. ; Landers ; E.M. ; McArdle ; P. ; Ní ; Chonchubhair ; N.
• 关键词：Organotin ; Organoantimony ; Adduct ; Mö ; ssbauer
• 刊名：Journal of Organometallic Chemistry
• 出版年：2000
• 出版时间：October 20, 2000
• 年：2000
• 卷：612
• 期：1-2
• 页码：53-60
• 全文大小：135 K

文摘

1:1 and 1:2 adducts of diphenyltin dichloride with triphenylphosphine oxide can be isolated in the solid state but the preparative conditions necessary to isolate an adduct of specific stoichiometry are difficult to define; none of acid: base ratio, choice of solvent or reaction temperature are significant factors. Adventitious crystal seeding probably has a dominant role. Both the 1:1 and 1:2 adducts of SnPh₂Cl₂, but only the 1:1 adduct of SnPh₂Br₂, were isolated. 1:1 and 1:2 adducts of both SnMe₂Cl₂ and SnBuⁿ₂Cl₂ were readily isolated whereas only 1:2 adducts were obtained with SnPh₂(NCS)₂ and SnBuⁿ₂(NCS)₂. SbPh₂Cl₃ readily forms a 1:1 adduct with triphenylphosphine oxide and the same adduct is obtained from the reaction of the phosphine oxide with SbPhCl₂. Crystallographic data are reported for SnPh₂Cl₂·OPPh₃, SnPh₂Cl₂·2OPPh₃, SnPh₂Br₂·OPPh₃ and SbPh₂Cl₃·OPPh₃. Both SnPh₂Cl₂·OPPh₃ and SnPh₂Br₂·OPPh₃ have tin in trigonal bipyramidal environments. ¹¹⁹Sn Mössbauer quadrupole splitting data are consistent with the same trigonal bipyramidal geometry for tin in SnMe₂Cl₂·OPPh₃ whereas the data for the butyl analogue suggest the presence of six-coordinated tin as a result of intermolecular Sn–Cl interactions. A notable feature of all of the adducts subjected to crystallographic studies is the presence of intramolecular π-interactions involving phenyl groups of the phosphine oxide and phenyl groups bonded to the metal.