Synthesis and catalytic properties of copper(I) complexes with imino- and aminophosphine ligands

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta Pub Date : 2025-08-30 DOI:10.1016/j.ica.2025.122884

Shuaicong Huo , Xuyan Bai , Piao Wang , Yujia Gao , Ying Yang

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引用次数: 0

Abstract

The iminophosphine ligands of o-Ph₂PC₆H₄-CH=N-p-R-C₆H₄ (P^N-imine for short; R = OMe (1, L¹ = MeO-ImP), Cl (2, L² = Cl-ImP), Br (3, L³ = Br-ImP), COOH (4, L⁴ = COOH-ImP)) and bridged [o-Ph₂PC₆H₄-CH=N]₂-R (bis(P^N-imine) for short; R = -C₂H₄- (5, L⁵ = Et-bisImP), -C₄H₈- (6, L⁶ = Bu-bisImP), -C₆H₁₂- (7, L⁷ = Hex-bisImP)) were synthesized starting from o-Ph₂PC₆H₄CHO with aryl/alkyl amines by condensation. In addition, amino derivatives of o-Ph₂PC₆H₄-CH₂-NH-p-R-C₆H₄ (P^NH-amine for short; R = Br (8, L⁸ = Br-AmP)) and bridged [o-Ph₂PC₆H₄-CH₂-NH]₂-R (bis(P^NH-amine) for short; R = -C₂H₄- (9, L⁹ = Et-bisAmP), -C₄H₈- (10, L¹⁰ = Bu-bisAmP), -C₆H₁₂- (11, L¹¹ = Hex-bisAmP)) were prepared by reduction of the imines (L^1–7) with NaBH₄. Treatment of imino- and aminophosphine ligands L^1–11 with [Cu(MeCN)₄]BF₄ yielded the corresponding copper(I) complexes [Cu(L^1–4)₂]BF₄ (1a-4a, L¹ = MeO-ImP, L² = Cl-ImP, L³ = Br-ImP, L⁴ = COOH-ImP), [Cu(L^5–7)]BF₄ (5a-7a, L⁵ = Et-bisImP, L⁶ = Bu-bisImP, L⁷ = Hex-bisImP), [Cu(L⁸)₂]BF₄ (8a, L⁸ = Br-AmP), and [Cu(L^9–11)]BF₄ (9a-11a, L⁹ = Et-bisAmP, L¹⁰ = Bu-bisAmP, L¹¹ = Hex-bisAmP), while Ni(II) analogues [Ni(L⁵)](PF₆)₂ (5b, L⁵ = Et-bisImP) and [Ni(L⁹)Cl]PF₆ (9b, L⁹ = Et-bisAmP) were prepared serving as comparators. The compositions and structures of the synthesized ligands and complexes were characterized with FT-IR and NMR spectroscopy and primarily single-crystal X-ray diffraction analyses. The resulting Cu(I) and Ni(II) complexes were evaluated as catalysts for the hydrosilylation of acetophenone under mild conditions. It is worth noting that the Cu(I) complex [Cu(L⁵)]BF₄ (5a, L⁵ = Et-bisImP) achieved 93 %–99 % conversion in catalytic hydrosilylation of various aromatic and aliphatic ketones under mild conditions.

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亚胺膦和氨基膦配体铜(I)配合物的合成及其催化性能

o-Ph2PC6H4-CH=N- P -R- c6h4（简称P^N-亚胺），R = OMe (1, L1 = MeO-ImP), Cl (2, L2 = Cl- imp), Br （3, L3 = Br- imp), COOH (4, L4 = COOH- imp)）和桥接[o-Ph2PC6H4-CH=N]2-R （bis（P^N-亚胺））的亚膦配体；R = - c2h4 - (5, L5 = Et-bisImP), - c4h8 - (6, L6 = Bu-bisImP), - c6h12 - (7, L7 = hexx - bisimp)))由o-Ph2PC6H4CHO与芳基/烷基胺缩合合成。此外，o-Ph2PC6H4-CH2-NH- P -R- c6h4（简称P^NH-amine； R = Br (8, L8 = Br- amp)）和桥接的[o-Ph2PC6H4-CH2-NH]2-R （bis(P^NH-amine)）的氨基衍生物；用NaBH4还原亚胺（L1-7），制得R = - c2h4 - (9, L9 = Et-bisAmP)、- c4h8 - (10, L10 = Bu-bisAmP)、- c6h12 - (11, L11 = hexx - bisamp)。用[Cu(MeCN)4]BF4处理亚胺和氨基膦配体L1 -11得到相应的铜(I)配合物[Cu(L1 -4)2]BF4 (1a-4a, L1 = MeO-ImP, L2 = Cl- imp, L3 = Br-ImP, L4 = COOH-ImP), [Cu(L5 -7)]BF4 (5a-7a, L5 = Et-bisImP, L6 = Bu-bisImP, L7 = Hex-bisImP), [Cu(L8)2]BF4 （8a, L8 = Br-AmP）和[Cu(L9 -11)]BF4 (9a-11a, L9 = Et-bisAmP, L10 = Bu-bisAmP, L11 = Hex-bisAmP)，而Ni（II）类似物[Ni(L5)](PF6)2 （5b, L5 = Et-bisImP）和[Ni(L9)Cl]PF6 (9b，L9 = Et-bisAmP)作为比较物。合成的配体和配合物的组成和结构通过红外光谱和核磁共振光谱以及主要的单晶x射线衍射分析进行了表征。在温和条件下评价了Cu(I)和Ni（II）配合物对苯乙酮硅氢化反应的催化作用。值得注意的是，Cu(I)配合物[Cu(L5)]BF4 （5a, L5 = Et-bisImP）在温和条件下催化各种芳酮和脂肪酮的硅氢化反应中转化率达到93% - 99%。

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来源期刊

Inorganica Chimica Acta 化学-无机化学与核化学

CiteScore

6.00

自引率

3.60%

发文量

440

审稿时长

35 days

期刊介绍： Inorganica Chimica Acta is an established international forum for all aspects of advanced Inorganic Chemistry. Original papers of high scientific level and interest are published in the form of Articles and Reviews. Topics covered include: • chemistry of the main group elements and the d- and f-block metals, including the synthesis, characterization and reactivity of coordination, organometallic, biomimetic, supramolecular coordination compounds, including associated computational studies; • synthesis, physico-chemical properties, applications of molecule-based nano-scaled clusters and nanomaterials designed using the principles of coordination chemistry, as well as coordination polymers (CPs), metal-organic frameworks (MOFs), metal-organic polyhedra (MPOs); • reaction mechanisms and physico-chemical investigations computational studies of metalloenzymes and their models; • applications of inorganic compounds, metallodrugs and molecule-based materials. Papers composed primarily of structural reports will typically not be considered for publication.