具有X[PtC≡CC≡CC≡CC≡C]PtX片段的线状二铂、三铂和四铂配合物；用于单分子性质测量的迭代合成与功能化。
Wire like diplatinum, triplatinum, and tetraplatinum complexes featuring X[PtC[triple bond, length as m-dash]CC[triple bond, length as m-dash]CC[triple bond, length as m-dash]CC[triple bond, length as m-dash]C]PtX segments; iterative syntheses and functionalization for measurements of single molecule properties.
作者信息
Zheng Qinglin, Schneider Jakob F, Amini Hashem, Hampel Frank, Gladysz John A
机构信息
Institut für Organische Chemie and Interdisciplinary Center for Molecular Materials, Friedrich-Alexander-Universität Erlangen-Nürnberg, Henkestraße 42, 91054 Erlangen, Germany.
出版信息
Dalton Trans. 2019 Apr 23;48(17):5800-5816. doi: 10.1039/c9dt00870e.
Reaction of (p-tol3P)2PtCl2 and Me3Sn(C[triple bond, length as m-dash]C)2SiMe3 (1 : 1/THF/reflux) gives monosubstituted trans-Cl(p-tol3P)2Pt(C[triple bond, length as m-dash]C)2SiMe3 (63%), which with wet n-Bu4N+ F- yields trans-Cl(p-tol3P)2Pt(C[triple bond, length as m-dash]C)2H (2, 96%). Hay oxidative homocoupling (O2/CuCl/TMEDA) gives all-trans-Cl(p-tol3P)2Pt(C[triple bond, length as m-dash]C)4Pt(Pp-tol3)2Cl (3, 68%). Reaction of 3 and Me3Sn(C[triple bond, length as m-dash]C)2SiMe3 (1 : 1/rt) affords monosubstituted all-trans-Cl(p-tol3P)2Pt(C[triple bond, length as m-dash]C)4Pt(Pp-tol3)2(C[triple bond, length as m-dash]C)2SiMe3 (46%), which is converted by a similar desilylation/homocoupling sequence to all-trans-Cl[(p-tol3P)2Pt(C[triple bond, length as m-dash]C)4]3Pt(Pp-tol3)2Cl (7; 79%). Reaction of (p-tol3P)2PtCl2 and excess H(C[triple bond, length as m-dash]C)2SiMe3 (HNEt2/cat. CuI) gives trans-Me3Si(C[triple bond, length as m-dash]C)2Pt(Pp-tol3)2(C[triple bond, length as m-dash]C)2SiMe3 (78%), which with wet n-Bu4N+ F- affords trans-H(C[triple bond, length as m-dash]C)2Pt(Pp-tol3)2(C[triple bond, length as m-dash]C)2H (96%). Hay oxidative cross coupling with 2 (1 : 4) gives all-trans-Cl[(p-tol3P)2Pt(C[triple bond, length as m-dash]C)4]2Pt(Pp-tol3)2Cl (10, 36%) along with homocoupling product 3 (33%). Reaction of 3 and Me3Sn(C[triple bond, length as m-dash]C)2SiMe3 (1 : 2/rt) yields all-trans-Me3Si(C[triple bond, length as m-dash]C)2(p-tol3P)2Pt(C[triple bond, length as m-dash]C)4Pt(Pp-tol3)2(C[triple bond, length as m-dash]C)2SiMe3 (17, 77%), which with wet n-Bu4N+ F- gives all-trans-H(C[triple bond, length as m-dash]C)2(p-tol3P)2Pt(C[triple bond, length as m-dash]C)4Pt(Pp-tol3)2(C[triple bond, length as m-dash]C)2H (96%). Reaction of 3 and excess Me3P gives all-trans-Cl(Me3P)2Pt(C[triple bond, length as m-dash]C)4Pt(PMe3)2Cl (4, 86%). A model reaction of trans-(p-tol)(p-tol3P)2PtCl and KSAc yields trans-(p-tol)(p-tol3P)2PtSAc (12, 75%). Similar reactions of 3, 7, 10, and 4 give all-trans-AcS[(R3P)2Pt(C[triple bond, length as m-dash]C)4]nPt(PR3)2SAc (76-91%). The crystal structures of 3, 17, and 12 are determined. The first exhibits a chlorine-chlorine distance of 17.42 Å; those in 10 and 7 are estimated as 30.3 Å and 43.1 Å.
（对甲苯基3膦）2氯化铂（(p-tol3P)2PtCl2）与三甲基锡乙炔基二甲基硅烷（Me3Sn(C[三键，键长用m破折号表示]C)2SiMe3）（1∶1/四氢呋喃/回流）反应生成单取代的反式-氯（对甲苯基3膦）2铂乙炔基二甲基硅烷（trans-Cl(p-tol3P)2Pt(C[三键，键长用m破折号表示]C)2SiMe3，产率63%），其与湿的四丁基铵氟化物反应生成反式-氯（对甲苯基3膦）2铂乙炔基二氢化物（2，产率96%）。海伊氧化均偶联反应（氧气/氯化铜/四甲基乙二胺）生成全反式-氯（对甲苯基3膦）2铂乙炔基四聚体铂（对甲苯基3膦）2氯（3，产率68%）。3与三甲基锡乙炔基二甲基硅烷（1∶1/室温）反应得到单取代的全反式-氯（对甲苯基3膦）2铂乙炔基四聚体铂（对甲苯基3膦）2乙炔基二甲基硅烷（产率46%），通过类似的脱硅基/均偶联序列将其转化为全反式-氯[（对甲苯基3膦）2铂乙炔基四聚体]3铂（对甲苯基3膦）2氯（7；产率79%）。（对甲苯基3膦）2氯化铂与过量的乙炔基二甲基硅烷氢化物（H(C[三键，键长用m破折号表示]C)2SiMe3）（二乙胺/催化量的碘化亚铜）反应得到反式-三甲基硅乙炔基二铂（对甲苯基3膦）2乙炔基二甲基硅烷（产率78%），其与湿的四丁基铵氟化物反应得到反式-氢乙炔基二铂（对甲苯基3膦）2乙炔基二氢化物（产率96%）。海伊氧化交叉偶联反应（与2，1∶4）生成全反式-氯[（对甲苯基3膦）2铂乙炔基四聚体]2铂（对甲苯基3膦）2氯（10，产率36%）以及均偶联产物3（产率33%）。3与三甲基锡乙炔基二甲基硅烷（1∶2/室温）反应生成全反式-三甲基硅乙炔基二（对甲苯基3膦）2铂乙炔基四聚体铂（对甲苯基3膦）2乙炔基二甲基硅烷（17，产率77%），其与湿的四丁基铵氟化物反应得到全反式-氢乙炔基二（对甲苯基3膦）2铂乙炔基四聚体铂（对甲苯基3膦）2乙炔基二氢化物（产率96%）。3与过量的三甲基膦反应得到全反式-氯（三甲基膦）2铂乙炔基四聚体铂（三甲基膦）2氯（4，产率86%）。反式-（对甲苯基）（对甲苯基3膦）2氯化铂与醋酸钾反应生成反式-（对甲苯基）（对甲苯基3膦）2铂硫代醋酸酯（12，产率75%）。3、7与10和4的类似反应得到全反式-硫代醋酸酯[（R3P）2铂乙炔基四聚体]n铂（PR3）2硫代醋酸酯（产率76 - 91%）。测定了3、17和12的晶体结构。第一个化合物中氯-氯距离为17.42 Å；10和7中的氯-氯距离估计分别为30.3 Å和43.1 Å。
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