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金、钴-ηPCO和铜-ηPCO配合物的分离，铱-ηPCO配合物向双金属二膦烯的转化，以及无相互作用的PCO阴离子。

Isolation of Au-, Co-ηPCO and Cu-ηPCO complexes, conversion of an Ir-ηPCO complex into a dimetalladiphosphene, and an interaction-free PCO anion.

作者信息

Liu Liu, Ruiz David A, Dahcheh Fatme, Bertrand Guy, Suter Riccardo, Tondreau Aaron M, Grützmacher Hansjörg

机构信息

UCSD-CNRS Joint Research Chemistry Laboratory (UMI 3555) , Department of Chemistry and Biochemistry , University of California San Diego , La Jolla , CA 92093-0343 , USA . Email:

Key Laboratory for Chemical Biology of Fujian Province , College of Chemistry and Chemical Engineering , Department of Chemistry , Xiamen University , Xiamen , 361005 , China.

出版信息

Chem Sci. 2016 Mar 1;7(3):2335-2341. doi: 10.1039/c5sc04504e. Epub 2016 Jan 4.

DOI:10.1039/c5sc04504e
PMID:29997776
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6003603/
Abstract

Sodium phosphaethynolate reacts with [MCl(PDI)] (M = Co, Ir; PDI = pyridinediimine) to give metallaphosphaketenes, which in the case of iridium rearranges into a dimetalladiphosphene, CO migration from phosphorus to the metal. Two different bonding modes of the PCO anion to CAAC-coinage metal complexes [CAAC: cyclic (alkyl)(amino)(carbene)] are reported, one featuring a strong Au-P bond and the other an η coordination to copper. The gold complex appears to be mostly unreactive whereas the copper complex readily reacts with various organic substrates. A completely free PCO anion was structurally characterized as the [Cu(L)] (OCP) salt. It results from the simple displacement of the PCO unit of the cationic (CAAC)Cu(PCO) complex by a second equivalent of CAAC.

摘要

磷乙炔酸钠与[MCl(PDI)]（M = Co，Ir；PDI = 吡啶二亚胺）反应生成金属磷杂环丁二烯，在铱的情况下会重排为双金属二磷烯，同时发生CO从磷向金属的迁移。报道了PCO阴离子与CAAC-贵金属配合物[CAAC：环状（烷基）（氨基）（卡宾）]的两种不同键合模式，一种具有强Au-P键，另一种是与铜的η配位。金配合物似乎大多无反应性，而铜配合物则容易与各种有机底物反应。一个完全游离的PCO阴离子被结构表征为Cu(L)盐。它是由第二个当量的CAAC简单取代阳离子（CAAC）Cu(PCO)配合物中的PCO单元而产生的。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d0e3/6003603/526628b454d5/c5sc04504e-f7.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d0e3/6003603/28ea777d6226/c5sc04504e-f1.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d0e3/6003603/c86415dc90f8/c5sc04504e-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d0e3/6003603/7a0373f65d01/c5sc04504e-f6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d0e3/6003603/526628b454d5/c5sc04504e-f7.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d0e3/6003603/28ea777d6226/c5sc04504e-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d0e3/6003603/7bc412fcf55d/c5sc04504e-f2.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d0e3/6003603/c86415dc90f8/c5sc04504e-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d0e3/6003603/7a0373f65d01/c5sc04504e-f6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d0e3/6003603/526628b454d5/c5sc04504e-f7.jpg

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