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双（喹啉-2-基甲基）苯基膦的硬币金属配合物——简单反应可产生前所未有的结果。

Coinage Metal Complexes of Bis(quinoline-2-ylmethyl)phenylphosphine-Simple Reactions Can Lead to Unprecedented Results.

作者信息

Kirst Christin, Tietze Jonathan, Mayer Peter, Böttcher Hans-Christian, Karaghiosoff Konstantin

机构信息

Department of Chemistry, Ludwig-Maximilians University of Munich, Butenandtstr. 5-13, (D) 81377, Munich, Germany.

出版信息

ChemistryOpen. 2022 Mar;11(3):e202100224. doi: 10.1002/open.202100224. Epub 2022 Feb 10.

DOI:10.1002/open.202100224
PMID:35146971
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8889507/
Abstract

The different coordination behavior of the flexible yet sterically demanding, hemilabile P,N ligand bis(quinoline-2-ylmethyl)phenylphosphine (bqmpp) towards selected Cu , Ag and Au species is described. The resulting X-ray crystal structures reveal interesting coordination geometries. With [Cu(MeCN) ]BF , compound 1 Cu (bqmpp) is obtained, wherein the copper(I) atoms display a distorted square planar and square pyramidal geometry. The steric demand and π-stacking of the ligand allow for a short Cu⋅⋅⋅Cu distance (2.588(9) Å). Cu complex 2 [Cu Cl (bqmpp) ]BF contains a rarely observed Cu Cl cluster, probably enabled by dichloromethane as the chloride source. In the cluster, even shorter Cu⋅⋅⋅Cu distances (2.447(1) Å) are present. The reaction of Ag[SbF ] with the ligand leads to a dinuclear compound (3) in solution as confirmed by P{ H} NMR spectroscopy. During crystallization, instead of the expected phosphine complex 3, a tris(quinoline-2-ylmethyl)bisphenyl-phosphine (tqmbp) compound Ag (tqmbp) 4 is formed by elimination of quinaldine. The Au(I) compound [Au (bqmpp) ]PF (5) is prepared as expected and shows a linear arrangement of two phosphine ligands around Au .

摘要

描述了柔性但空间要求较高的半不稳定P，N配体双（喹啉-2-基甲基）苯基膦（bqmpp）对选定的铜、银和金物种的不同配位行为。所得的X射线晶体结构揭示了有趣的配位几何形状。与[Cu(MeCN)₄]BF₄反应，得到化合物1 Cu₂(bqmpp)₂₂，其中铜（I）原子呈现扭曲的平面正方形和四方锥几何形状。配体的空间要求和π堆积使得铜····铜距离较短（2.588(9) Å）。铜配合物2 [Cu₂Cl₂(bqmpp)₂]BF₄包含一个很少观察到的Cu₂Cl₂簇，这可能是由于二氯甲烷作为氯源所致。在该簇中，存在甚至更短的铜···铜距离（2.447(1) Å）。Ag[SbF₆]与该配体的反应在溶液中生成一种双核化合物（3），³¹P{¹H} NMR光谱证实了这一点。在结晶过程中，形成的不是预期的膦配合物3，而是通过消除喹哪啶形成了三（喹啉-2-基甲基）双苯基膦（tqmbp）化合物Ag₂(tqmbp)₂₂ 4。金（I）化合物[Au₂(bqmpp)₂]PF₆（5）按预期制备，并且显示出两个膦配体围绕金呈线性排列。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/45d7/8889507/d57858ec215a/OPEN-11-e202100224-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/45d7/8889507/05fa81ccf11c/OPEN-11-e202100224-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/45d7/8889507/4c0de993ea98/OPEN-11-e202100224-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/45d7/8889507/cf81a628be0c/OPEN-11-e202100224-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/45d7/8889507/d7901c8bdd13/OPEN-11-e202100224-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/45d7/8889507/23c80845b669/OPEN-11-e202100224-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/45d7/8889507/b3a1217a7e0a/OPEN-11-e202100224-g011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/45d7/8889507/a81e840f94b9/OPEN-11-e202100224-g013.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/45d7/8889507/0bc317261b0c/OPEN-11-e202100224-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/45d7/8889507/d57858ec215a/OPEN-11-e202100224-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/45d7/8889507/05fa81ccf11c/OPEN-11-e202100224-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/45d7/8889507/4c0de993ea98/OPEN-11-e202100224-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/45d7/8889507/cf81a628be0c/OPEN-11-e202100224-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/45d7/8889507/d7901c8bdd13/OPEN-11-e202100224-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/45d7/8889507/23c80845b669/OPEN-11-e202100224-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/45d7/8889507/b3a1217a7e0a/OPEN-11-e202100224-g011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/45d7/8889507/a81e840f94b9/OPEN-11-e202100224-g013.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/45d7/8889507/0bc317261b0c/OPEN-11-e202100224-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/45d7/8889507/d57858ec215a/OPEN-11-e202100224-g008.jpg

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