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2-膦基苯硫醇金属配合物（M = Zn、Sn 和 Pb）：配体折叠和半配位的深入研究。

Metal complexes (M = Zn, Sn, and Pb) of 2-phosphinobenzenethiolates: insights into ligand folding and hemilability.

机构信息

Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, United States.

出版信息

Inorg Chem. 2013 Sep 3;52(17):9875-84. doi: 10.1021/ic400990n. Epub 2013 Aug 12.

DOI:10.1021/ic400990n
PMID:23937328
Abstract

The divalent metal complexes M(II){(SC6H4-2-PR2)-κ(2)S,P}2 (3-7, and 9-11) (M = Zn, Sn, or Pb; R = (i)Pr, (t)Bu, or Ph), the Sn(IV) complexes Sn{(SC6H4-2-PR2)-κ(2)-S,P}Ph2Cl (12 and 13) (R = (i)Pr and (t)Bu), and the ionic Sn(IV) complexes [Sn{(SC6H4-2-PR2)-κ(2)-S,P}Ph2][BPh4] (14 and 15) (R = (i)Pr and (t)Bu) have been prepared and characterized by multinuclear NMR spectroscopy and single crystal X-ray diffraction when suitable crystals were afforded. The Sn(II) and Pb(II) complexes with R = Ph, (i)Pr, or (t)Bu (5, 6, 9, and 10) demonstrated ligand "folding" hinging on the P,S vector-a behavior driven by the repulsions of the metal/phosphorus and metal/sulfur lone pairs and increased M-S sigma bonding strength. This phenomenon was examined by density functional theory (DFT) calculations for the compounds in both folded and unfolded states. The Sn(IV) compound 13 (R = (t)Bu) crystallized with the phosphine in an axial position of the pseudotrigonal bipyramidal complex and also exhibited hemilability in the Sn-P dative bond, while compound 12 (R = (i)Pr), interestingly, crystallized with phosphine in an equatorial position and did not show hemilability. Finally, the crystal structure of 15 (R = (t)Bu) revealed the presence of an uncommon, 4-coordinate, stable Sn(IV) cation.

摘要

标题

二价金属配合物 M(II){(SC6H4-2-PR2)-κ(2)S,P}2 (3-7, 9-11) (M = Zn, Sn, 或 Pb; R = (i)Pr, (t)Bu, 或 Ph)、Sn(IV)配合物 Sn{(SC6H4-2-PR2)-κ(2)-S,P}Ph2Cl (12 和 13) (R = (i)Pr 和 (t)Bu) 以及离子型 Sn(IV)配合物 [Sn{(SC6H4-2-PR2)-κ(2)-S,P}Ph2][BPh4] (14 和 15) (R = (i)Pr 和 (t)Bu) 已被制备并通过多核 NMR 光谱和单晶 X 射线衍射进行了表征，在获得合适的晶体时进行了这些研究。当 R = Ph、(i)Pr 或 (t)Bu 时，Sn(II)和 Pb(II)配合物 5、6、9 和 10 表现出配体“折叠”现象，这一现象取决于 P、S 矢量——这是由金属/磷和金属/硫孤对的排斥以及增加的 M-S sigma 键强度驱动的。这一现象通过折叠和未折叠状态下化合物的密度泛函理论 (DFT) 计算进行了研究。化合物 13 (R = (t)Bu) 以轴向位置的膦原子结晶，在假三角双锥配合物中表现出配位键的单侧配体性，同时在 Sn-P 配位键中也表现出单侧配体性；而有趣的是，化合物 12 (R = (i)Pr) 以平面四方位置的膦原子结晶，且不表现出单侧配体性。最后，15 (R = (t)Bu) 的晶体结构显示出存在一种罕见的、四配位的、稳定的 Sn(IV)阳离子。

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