Tris(pentafluoroethyl)difluorophosphorane for Fluoride Abstraction and Ligand Exchange Reactions of N-Heterocyclic Carbene and Cyclic Alkyl(amino)carbene Copper(I) Fluorides

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions Pub Date : 2025-05-15 DOI:10.1039/d5dt00904a

Melanie Riethmann, Steffen A. Föhrenbacher, Christian Luz, Nikolai Ignat'ev, Maik Finze, Udo Radius

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引用次数: 0

Abstract

The synthesis and structural characterization of a variety N-heterocyclic carbene (NHC)- and cyclic (alkyl)(amino)carbene (cAAC)-ligated cationic copper(I) complexes, featuring the weakly coordinating tris(pentafluoroethyl)-trifluorophosphate counteranion (FAP− anion, [(C2F5)3PF3]−). Starting with the complex [(IDipp)Cu(C6Me6)]+FAP− (IIa) reported previously,1 a series of mononuclear complexes [(IDipp)Cu(LB)]+FAP− ((IDipp = 1,3-bis(2,6-di-iso-propylphenyl)-imidazolin-2-ylidene) was obtained via ligand exchange of C6Me6 with neutral two valence electron (2 VE) donor molecules (LB = NH3, 1; C6H12N2 = DABCO, 2; C7H10N2 = DMAP, 3; C4H4N2 = pyrazine, 4; C13H9N = acridine, 5; η1-O=C13H9N = acridone, 6; C4H10S = SEt2, 7; C4H8S = THT, 8; PCy3, 9), alongside the dinuclear species [{(IDipp)Cu}2(C2H3N3)2]2+2FAP− (10) with 1,2,4-triazole. In a parallel strategy, [(cAACMe)Cu(C6Me6)]+FAP− (IIb) was employed as precursor for Cu(I) complex formation, leading to [(cAACMe)Cu(LB)]+FAP− (LB = C7H10N2, 13; C4H10S, 14) and the dinuclear complexes [{(cAACMe)Cu}2{C6H12N2}]2+2FAP− (11) and [{(cAACMe)Cu}2{C4H4N2}]2+2FAP− (12). Additionally, the reaction of [(carbene)CuF] with (C2F5)3PF2 in the presence of different 2 VE donor ligands induced fluoride replacemant with a 2 VE donor ligand (LB). This strategy facilitated the isolation of a broad range of complexes of the type [(carbene)Cu(LB)]+FAP−, including [(IDipp)Cu(LB)]+FAP− (LB = (N≡CMe)2, 16; N≡CPh, 17; NH2Ph, 18; NHPh2, 21; NC5H5, 22; NC5H3F2, 24; NC5H2F3, 25; η1-O=CPh2, 27), [(SIDipp)Cu(NH2Ph)]+FAP− (19) (SIDipp = 1,3-bis(2,6-di-iso-propylphenyl)-imidazolidin-2-ylidene) and [(cAACMe)Cu(LB)]+FAP− (cAACMe = 1-(2,6-di-iso-propylphenyl)-3,3,5,5-tetramethyl-pyrrolidin-2-ylidene; LB = N≡CMe, 15; NH2Ph, 20; NC5H5, 23; THF, 28). Additionally, the dinuclear complex [{(IDipp)Cu(μ-ONC5H5)}2]2+2FAP− (26) was obtained upon reaction with pyridine-N-oxide. In all cases the carbene ligand stayed intact and the formation of Lewis acid/base pairs of the 2VE ligand and (C2F5)3PF2 was never observed. As a result, mixtures of [(carbene)CuF] and (C2F5)3PF2 may serve as synthon for [(carbene)Cu]+, as demonstrated in this work.

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三（五氟乙基）二氟磷烷用于n -杂环卡宾和环烷基（氨基）卡宾铜(I)氟化物的氟提取和配体交换反应

以弱配位三（五氟乙基）-三氟磷酸反阴离子（FAP−阴离子，[(C2F5)3PF3]−）为特征的n -杂环卡宾(NHC)-和环（烷基）（氨基）卡宾(cAAC)-阳离子铜(I)配合物的合成和结构表征。从先前报道的络合物[(IDipp)Cu(C6Me6)]+FAP−(IIa) 1开始，通过C6Me6与中性二价电子（2 VE）供体分子(LB = nh3,1；C6h12n2 = dabco, 2；C7h10n2 = dmap, 3；C4H4N2 =吡嗪，4；C13H9N =吖啶，5；η1-O=C13H9N =吖啶酮，6；C4H10S = SEt2, 7；C4h8s = t, 8；pcy3,9)，与双核物种[{(IDipp)Cu}2(C2H3N3)2]2+2FAP−(10)与1,2,4-三唑。在平行策略中，[(cAACMe)Cu(C6Me6)]+FAP−(IIb)作为Cu(I)络合物形成的前驱体，得到[(cAACMe)Cu(LB)]+FAP−(LB = C7H10N2, 13；C4H10S, 14)和双核配合物[{(cAACMe)Cu}2{C6H12N2}]2+2FAP−(11)和[{(cAACMe)Cu}2{C4H4N2}]2+2FAP−（12）此外，[(carbene)CuF]与（C2F5）3PF2在不同的2 VE给体存在下的反应诱导氟被2 VE给体取代（LB）。这一策略有助于广泛分离[(carbene)Cu(LB)]+FAP−类型的配合物，包括[(IDipp)Cu(LB)]+FAP−(LB = (N≡CMe) 2,16；N≡CPh 17;NH2Ph 18;NHPh2 21;NC5H5 22;NC5H3F2 24;NC5H2F3 25;η1-O= cph2,27), [(SIDipp)Cu(NH2Ph)]+FAP−(19)（SIDipp = 1,3-二（2,6-二异丙基苯基）-咪唑烷-2-乙基）和[(cAACMe)Cu(LB)]+FAP−（cAACMe = 1-（2,6-二异丙基苯基）-3,3,5,5-四甲基吡啶烷-2-乙基）；LB = N≡CMe, 15；NH2Ph 20;NC5H5 23;四氢呋喃,28)。与吡啶- n -氧化物反应得到双核配合物[{(IDipp)Cu(μ-ONC5H5)}2]2+2FAP−(26)。在所有情况下，碳烯配体保持完整，并且从未观察到2VE配体和（C2F5）3PF2的刘易斯酸/碱基对的形成。因此，[(carbene)CuF]和（C2F5）3PF2的混合物可以作为[(carbene)Cu]+的合成物，正如本研究所证明的那样。

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来源期刊

Dalton Transactions 化学-无机化学与核化学

CiteScore

6.60

自引率

7.50%

发文量

1832

审稿时长

1.5 months

期刊介绍： Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.