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Cyclic Platina(borasiloxane)s and Platina(siloxane)s and Their Chemical Properties
Organometallics ( IF 2.8 ) Pub Date : 2017-12-26 00:00:00 , DOI: 10.1021/acs.organomet.7b00690 Hiroki Noda 1 , Kimiya Tanaka 1 , Makoto Tanabe 1 , Kohtaro Osakada 1
Organometallics ( IF 2.8 ) Pub Date : 2017-12-26 00:00:00 , DOI: 10.1021/acs.organomet.7b00690 Hiroki Noda 1 , Kimiya Tanaka 1 , Makoto Tanabe 1 , Kohtaro Osakada 1
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[Pt(SiHPh2)2(dmpe)] (dmpe = 1,2-bis(dimethylphosphino)ethane) reacts with arylboronic acids to produce six-membered platinacycles [
Pt(SiPh2-O-BAr-O-
SiPh2)(dmpe)] (Ar = C6H4-4-COMe (1a), C6H4-4-CF3 (1b)). X-ray crystallography of 1a revealed the structure having a planar six-membered ring, composed of Pt, O, B, and Si atoms. Reaction of H2O with [Pt(SiHPh2)2(dmpe)] formed a four-membered cyclic complex, [Pt(SiPh2-O-SiPh2)(dmpe)] (2), which was observed in the initial reaction mixture of 4-acetylphenylboronic acid with [Pt(SiHPh2)2(dmpe)]. Exposure of solutions of [Pt(SiHPh2)2(dmpe)] and of [Pt(SiHAr2)2(PMe3)2] (Ar = Ph, C6H4-4-Me) to air resulted in the formation of the cyclic platina(siloxane)s, [Pt(O-SiPh2-O-SiPh2-O)(dmpe)] (3) and [Pt(O-SiAr2-O-SiAr2-O)(PMe3)2] (4: Ar = Ph; 5: Ar = C6H4-4-Me), respectively. The six-membered platina(borasiloxane) 1a reacts with H2GePh2 and with CF3CO2H to release the cyclic borasiloxanes as the products. The former reaction affords [Pt(GeHPh2)2(dmpe)], while the latter produces [Pt(OCOCF3)2(dmpe)] as the Pt-containing products. A similar reaction of HCl with platina(siloxane) 4 gives a disiloxanediol via cleavage of the Pt–O bonds. Complex 4 reacts with H2SiPh2 to form a triplatinum complex, [{Pt(PMe3)}3(μ-SiPh2)3] (15), which is obtained under milder conditions than the previously reported reaction starting from [Pt(SiHPh2)2(PMe3)2].
中文翻译：
环状Platina（硼硅氧烷）和Platina（硅氧烷）及其化学性质
[Pt（SiHPh 2）2（dmpe）]（dmpe = 1,2-双（二甲基膦基）乙烷）与芳基硼酸反应生成六元铂环化合物[ Pt（SiPh 2 -O-BAr-O- SiPh 2）（ dmpe）]（Ar = C 6 H 4 -4-COMe（1a），C 6 H 4 -4-CF 3（1b））。1a的X射线晶体学分析显示该结构具有一个平面的六元环，该环由Pt，O，B和Si原子组成。H 2 O与[Pt（SiHPh 2）2（dmpe）]的反应形成四元环状络合物，[ Pt（SiPh2 -OS IPH 2）（DMPE）]（2），这是在4-乙酰基苯基硼酸与初始反应混合物观察到的Pt（SiHPh 2）2（DMPE）]。[Pt（SiHPh 2）2（dmpe）]和[Pt（SiHAr 2）2（PMe 3）2 ]（Ar = Ph，C 6 H 4 -4-Me）的溶液暴露在空气中导致形成环状粗铂的（硅氧烷），[铂（O-SIPH 2 -O-SIPH 2 -O）（DMPE）]（3）和[铂（O-SIAR 2 -O-SIAR 2 -O）（PMe 3）2 ]（4：Ar = Ph; 5：Ar = C 6 H 4 -4-Me）。六元铂（硼硅氧烷）1a与H 2 GePh 2和CF 3 CO 2 H反应，释放出环状硼硅氧烷作为产物。前者反应提供[Pt（GeHPh 2）2（dmpe）]，而后者产生[Pt（OCOCF 3）2（dmpe）]为含Pt产物。HCl与铂（硅氧烷）4的类似反应通过Pt–O键的裂解得到二硅氧烷二醇。复杂的4分发生反应用H 2 SIPH 2以形成triplatinum络合物，[{的Pt（PME 3）} 3（μ-SIPH 2）3 ]（15），其比以前报道的反应更温和的条件下得到由[PT开始（ SiHPh 2）2（PMe 3）2 ]。
更新日期：2017-12-27
Pt(SiPh2-O-BAr-O-SiPh2)(dmpe)] (Ar = C6H4-4-COMe (1a), C6H4-4-CF3 (1b)). X-ray crystallography of 1a revealed the structure having a planar six-membered ring, composed of Pt, O, B, and Si atoms. Reaction of H2O with [Pt(SiHPh2)2(dmpe)] formed a four-membered cyclic complex, [Pt(SiPh2-O-SiPh2)(dmpe)] (2), which was observed in the initial reaction mixture of 4-acetylphenylboronic acid with [Pt(SiHPh2)2(dmpe)]. Exposure of solutions of [Pt(SiHPh2)2(dmpe)] and of [Pt(SiHAr2)2(PMe3)2] (Ar = Ph, C6H4-4-Me) to air resulted in the formation of the cyclic platina(siloxane)s, [Pt(O-SiPh2-O-SiPh2-O)(dmpe)] (3) and [Pt(O-SiAr2-O-SiAr2-O)(PMe3)2] (4: Ar = Ph; 5: Ar = C6H4-4-Me), respectively. The six-membered platina(borasiloxane) 1a reacts with H2GePh2 and with CF3CO2H to release the cyclic borasiloxanes as the products. The former reaction affords [Pt(GeHPh2)2(dmpe)], while the latter produces [Pt(OCOCF3)2(dmpe)] as the Pt-containing products. A similar reaction of HCl with platina(siloxane) 4 gives a disiloxanediol via cleavage of the Pt–O bonds. Complex 4 reacts with H2SiPh2 to form a triplatinum complex, [{Pt(PMe3)}3(μ-SiPh2)3] (15), which is obtained under milder conditions than the previously reported reaction starting from [Pt(SiHPh2)2(PMe3)2].
中文翻译：
环状Platina（硼硅氧烷）和Platina（硅氧烷）及其化学性质
[Pt（SiHPh 2）2（dmpe）]（dmpe = 1,2-双（二甲基膦基）乙烷）与芳基硼酸反应生成六元
铂环化合物[ Pt（SiPh 2 -O-BAr-O- SiPh 2）（ dmpe）]（Ar = C 6 H 4 -4-COMe（1a），C 6 H 4 -4-CF 3（1b））。1a的X射线晶体学分析显示该结构具有一个平面的六元环，该环由Pt，O，B和Si原子组成。H 2 O与[Pt（SiHPh 2）2（dmpe）]的反应形成四元环状络合物，[ Pt（SiPh2 -OS IPH 2）（DMPE）]（2），这是在4-乙酰基苯基硼酸与初始反应混合物观察到的Pt（SiHPh 2）2（DMPE）]。[Pt（SiHPh 2）2（dmpe）]和[Pt（SiHAr 2）2（PMe 3）2 ]（Ar = Ph，C 6 H 4 -4-Me）的溶液暴露在空气中导致形成环状粗铂的（硅氧烷），[铂（O-SIPH 2 -O-SIPH 2 -O）（DMPE）]（3）和[铂（O-SIAR 2 -O-SIAR 2 -O）（PMe 3）2 ]（4：Ar = Ph; 5：Ar = C 6 H 4 -4-Me）。六元铂（硼硅氧烷）1a与H 2 GePh 2和CF 3 CO 2 H反应，释放出环状硼硅氧烷作为产物。前者反应提供[Pt（GeHPh 2）2（dmpe）]，而后者产生[Pt（OCOCF 3）2（dmpe）]为含Pt产物。HCl与铂（硅氧烷）4的类似反应通过Pt–O键的裂解得到二硅氧烷二醇。复杂的4分发生反应用H 2 SIPH 2以形成triplatinum络合物，[{的Pt（PME 3）} 3（μ-SIPH 2）3 ]（15），其比以前报道的反应更温和的条件下得到由[PT开始（ SiHPh 2）2（PMe 3）2 ]。
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