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首页> 外文期刊>Chemistry: A European journal >Insertion of Alkynes into the Pt-Si Bond of Silylplatinum Complexes Leading to the Formation of 4-Sila-3-platinacyclobutenes and 5-Sila-2-platina-1,4-cyclohexadienes
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Insertion of Alkynes into the Pt-Si Bond of Silylplatinum Complexes Leading to the Formation of 4-Sila-3-platinacyclobutenes and 5-Sila-2-platina-1,4-cyclohexadienes

机译：炔烃插入硅铂络合物的Pt-Si键中导致形成4-Sila-3-platinacyclobutenes和5-Sila-2-platina-1,4-cyclohexadienes

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摘要

The reaction of dimethyl acetylenedicarboxylate (DMAD) with [Pt(SiHPh_2)_2(PMe_3)_2] produces cis[Pt(CZ=CZ-SiHPh_2)(SiHPh_2)(PMe_3)_2] (cis-1,Z=COOMe) and [Pt(CZ=CZ-SiPh_2)(PMe_3)_2] (2) depending on the reaction conditions.cis-1 and 2 are equilibrated in solution at room temperature,and they are isolated by recrystallization of the mixtures.cis-1 is converted slowly in solution into trans[Pt(CZ=CZ-SiHPh_2)(SiHPh_2)(PMe_3)_2] (trans-1) via intermediate 2 followed by reaction with H_2SiPh_2.DMAD also reacts with [Pt(SiHPh_2)_2(dmpe)](dmpe=1,2-bis(dimethylphosphino)ethane) to afford [Pt(CZ=CZ-SiHPh_2)-(SiHPh_2)dmpe)] (3).Conversion 3 into 4-sila-3-platinacyclobutene [Pt(CZ=CZ-SiPh_2)(dmpe)] (4) takes place,accomopanied by formation of H_2SiPh_2,to give an equilibrated mixture of the two complexes.Crystallo-graphic and spectroscopic data of cis-1,trans-1,and 3 suggest the presence of an intramolecular interaction between the Si-H group of the 3-silia-1-propenyl ligand and Pt via an Si-H-Pt three-center-four-electron bond in the solid state and in solution.DMAD reacts with 2 to give 5-sila-2-platina-1,4-cyclohexadiene with pi-coordinated DMAD,[Pt(CZ=CZ-SiPh_2-CZ=CZ)(DMAD)-(PMe_3)_2] (5),which is also obtained from the reaction of excess DMAD with [Pt(SiHPh_2)_2(PMe_3)_2].Unsymmetrical six-membered silaplatinacycles without pi-coordinated alkyne,[Pt(CZ=CZ-SiPh_2-CH=CX)(PMe_3)_2] (6;X=COOMe;7:X=Ph),are prepared analogously from the respective reactions of phenyl acetylene and of methyl acetylene carboylxate with 2.Methyl 2-butynolate reacts with 2 at 50 deg C to form a mixture of the regioisomers [Pt(CZ=CZ-SiPh_2-CMe=CZ)(PMe_3)_2] (8) and [Pt(CZ=CZ-SiPh_2-CZ=CMe)-(PMe_3)_2] (9).
机译：乙炔二甲酸二甲酯（DMAD）与[Pt（SiHPh_2）_2（PMe_3）_2]的反应生成顺式[Pt（CZ = CZ-SiHPh_2）（SiHPh_2）（PMe_3）_2]（cis-1，Z = COOMe）和[ Pt（CZ = CZ-SiPh_2）（PMe_3）_2]（2）取决于反应条件。在室温下将顺式1和顺式2平衡在溶液中，并通过混合物的重结晶进行分离。顺式1转化经由中间体2在溶液中缓慢转化为trans [Pt（CZ = CZ-SiHPh_2）（SiHPh_2）（PMe_3）_2]（trans-1），然后与H_2SiPh_2反应。DMAD也与[Pt（SiHPh_2）_2（dmpe）]反应（dmpe ＝ 1，2-双（二甲基膦基）乙烷）得到[Pt（CZ ＝ CZ-SiHPh_2）-（SiHPh_2）dmpe）]（3）。将3转化为4-sila-3-铂环丁烯[Pt（CZ = CZ-SiPh_2）（dmpe）]（4）发生，伴随形成H_2SiPh_2，得到两种络合物的平衡混合物。cis-1，trans-1和3的晶体学和光谱数据表明存在Si-HP分析3-silia-1-丙烯基配体的Si-H基团与Pt之间的分子内相互作用固态和溶液中的三中心四电子键。DMAD与2反应生成带有pi配位DMAD的5-sila-2-platina-1,4-环己二烯，[Pt（CZ = CZ-SiPh_2 -CZ = CZ）（DMAD）-（PMe_3）_2]（5），这也是通过过量DMAD与[Pt（SiHPh_2）_2（PMe_3）_2]的反应获得的。不具有pi配位的不对称六元硅氨铂环炔烃[Pt（CZ = CZ-SiPh_2-CH = CX）（PMe_3）_2]（6; X = COOMe; 7：X = Ph）的制备方法类似地由苯基乙炔和甲基乙炔羰基甲酸酯与2. 2-丁酸甲酯在50℃与2反应形成区域异构体[Pt（CZ = CZ-SiPh_2-CMe = CZ）（PMe_3）_2]（8）和[Pt（CZ = CZ-SiPh_2）的混合物-CZ = CMe）-（PMe_3）_2]（9）。

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