Department of Chemistry, Tulane University, 6400 Freret Street, New Orleans 70118-5698, USA.
Inorg Chem. 2012 Jun 18;51(12):6567-76. doi: 10.1021/ic300124n. Epub 2012 Apr 6.
A synthesis of 1-(thioacetyl)triptycene (5), a convenient protected form of 1-(thiolato)triptycene STrip, is described, a key transformation being the high yield conversion of tert-butyl 1-triptycenyl sulfide (8) to 5 by a protocol employing BBr(3)/AcCl. Syntheses of the two-coordinate copper(I) compounds [Bu(4)N][Cu(STrip)(2)], [Bu(4)N]10, and [(Cu(IMes)(STrip)] (13) proceed readily by chloride displacement from CuCl and [Cu(IMes)Cl], respectively. Reaction of 10 with Ph(3)SiSH or Me(3)SiI produces the heteroleptic species Cu(STrip)(SSiPh(3)) (11) and Cu(STrip)I (12), detected by mass spectrometry, in mixture with the homoleptic bis(thiolate) anions. Structural identification by X-ray crystallography of the ligand precursor molecules 9-(thioacetyl)anthracene (4, triclinic and orthorhombic polymorphs), tert-butyl 9-anthracenyl sulfide (7), 5, and tert-butyl 1-triptycenyl sulfide (8) are presented. Crystallographic characterization of bis(9-anthracenyl)sulfide (3), which features a C-S-C angle of 104.0° and twist angle of 54.8° between anthracenyl planes, is also given. A crystal structure of [Bu(4)N][(STrip)], [Bu(4)N]9, provides an experimental measure of 144.6° for the ligand cone angle. The crystal structures of [Bu(4)N]10 and 13 are reported, the former of which reveals an unexpectedly small C-S···S-C torsion angle of ∼41° (average of two values), which confers a near "cis" disposition of the triptycenyl groups with respect the S-Cu-S axis. This conformation is governed by interligand π···π and CH···π interactions. A crystal structure of an adventitious product, [Bu(4)N][(Cu-STrip)(6)(μ(6)-Br)]·[Bu(4)N][PF(6)], [Bu(4)N]14·[Bu(4)N][PF(6)] is described, which reveals a cyclic hexameric structure previously unobserved in cuprous thiolate chemistry. The Cu(6)S(6) ring displays a centrosymmetric cyclohexane chair type conformation with a Br(-) ion residing at the inversion center and held in place by apparent soft-soft interactions with the Cu(I) ions.
一种 1-(硫代乙酰基)三环[3.3.1.13,7]癸烷（5）的合成方法，1-(硫醇基)三环[3.3.1.13,7]癸烷STrip的一种方便的保护形式，是一个关键的转化，即用 BBr(3)/AcCl 进行高收率的 tert-butyl 1-三环癸基硫化物（8）转化为 5。铜（I）配合物[Bu(4)N][Cu(STrip)(2)]、[Bu(4)N]10 和[(Cu(IMes)(STrip)]（13）的合成通过 CuCl 和[Cu(IMes)Cl]的氯化物取代反应很容易进行。10 与 Ph(3)SiSH 或 Me(3)SiI 的反应产生了杂配体物种Cu(STrip)(SSiPh(3))（11）和Cu(STrip)I（12），通过质谱检测到，与同核双（硫醇）阴离子混合。通过 X 射线晶体学对配体前体分子 9-(硫代乙酰基)蒽（4，三斜晶系和正交晶系多晶型物）、tert-butyl 9-蒽基硫化物（7）、5 和 tert-butyl 1-三环癸基硫化物（8）进行了结构鉴定。还给出了双（9-蒽基）硫化物（3）的晶体结构特征，其 C-S-C 角为 104.0°，蒽基平面之间的扭转角为 54.8°。[Bu(4)N][(STrip)]、[Bu(4)N]9 的晶体结构提供了配体锥角为 144.6°的实验测量值。报道了[Bu(4)N]10 和 13 的晶体结构，前者显示出出乎意料的小 C-S···S-C 扭转角约为 41°（两个值的平均值），这赋予了三环癸基基团相对于 S-Cu-S 轴的近乎“顺式”构象。这种构象受配体π···π和 CH···π相互作用的控制。描述了一种偶然产物[Bu(4)N][(Cu-STrip)(6)(μ(6)-Br)]·[Bu(4)N][PF(6)]·[Bu(4)N]14·[Bu(4)N][PF(6)]的晶体结构，该结构揭示了以前在亚铜硫醇化学中未观察到的环状六聚体结构。Cu(6)S(6)环呈现出对称的环己烷椅型构象，其中 Br(-)离子位于反演中心，并通过与 Cu(I)离子的明显软-软相互作用而固定在位。
