sp Carbon Chains Surrounded by sp<sup>3</sup> Carbon Double Helices: Coordination-Driven Self-Assembly of Wirelike Pt(C⋮C)<i><sub>n</sub></i>Pt Moieties That Are Spanned by Two P(CH<sub>2</sub>)<i><sub>m</sub></i>P Linkages
作者:Jürgen Stahl、Wolfgang Mohr、Laura de Quadras、Thomas B. Peters、James C. Bohling、José Miguel Martín-Alvarez、Gareth R. Owen、Frank Hampel、John A. Gladysz
DOI:10.1021/ja0716103
日期:2007.7.1
trans-(C6F5)(p-tol3P)2Pt(CC)4Pt(Pp-tol3)2(C6F5) and diphosphines Ar2P(CH2)mPAr2 yield trans,trans-(C6F5)(Ar2P(CH2)mPAr2)Pt(CC)4Pt(Ar2P(CH2)mPAr2)(C6F5), in which the platinum atoms are spanned via an sp and two sp3 carbon chains (Ar/m = 3, Ph/14, 87%; 4, p-tol/14, 91%; 5, p-C6H4-t-Bu/14, 77%; 7, Ph/10, 80%; 8, Ph/11, 80%; 9, Ph/12, 36%; only oligomers form for m > 14). Crystal structures of 3-5 show that the sp3
trans,trans-(C6F5)(p-tol3P)2Pt(CC)4Pt(Pp-tol3)2(C6F5)和二膦Ar2P(CH2)mPAr2的反应产生trans,trans-(C6F5)(Ar2P(CH2)mPAr2) Pt(CC)4Pt(Ar2P(CH2)mPAr2)(C6F5),其中铂原子通过一个 sp 和两个 sp3 碳链跨越(Ar/m = 3, Ph/14, 87%; 4, p-tol /14, 91%; 5, p-C6H4-t-Bu/14, 77%; 7, Ph/10, 80%; 8, Ph/11, 80%; 9, Ph/12, 36%; 仅低聚物m > 14 的形式)。3-5 的晶体结构表明 sp3 链采用手性双螺旋构象,在大约范德华距离处屏蔽 sp 链,两个对映异构体都在晶胞中。铂金方形平面定义的角度为 196.6 度 -189.9 度或超过一半的扭曲。7-9 的晶体结构具有较短的