Synthesis and Alkyne Metathesis Activity of Rhenium Carbyne Complexes with PS-Chelating Ligands

IF 2.2 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

European Journal of Inorganic Chemistry Pub Date : 2025-01-26 DOI:10.1002/ejic.202400811

Long Yiu Tsang, Lam Cheung Kong, Herman H. Y. Sung, Ian D. Williams, Guochen Jia

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Abstract

Inspired by the catalytic alkyne metathesis activity of Re(V) carbyne complexes supported by phosphinophenolate (PO) ligands, new Re(V) carbyne complexes with analogous phoshorus-sulfur hybrid chelating ligands were synthesized. Treatment of Re(≡CR)Cl₂(PMePh₂)₃ (R = CH₂Ph, Ph) with (2-thiophenyl)diphenylphosphine (Ph₂P-o-C₆H₄SH, PSH) in the presence of NEt₃ produced the six-coordinated PS complexes Re(≡CR)(PMePh₂)(PS)₂ (PS = Ph₂P-o-C₆H₄S), which reacted with [(η⁶-cymene)RuCl₂]₂ to give five-coordinated trigonal bipyramidal complexes Re(≡CR)(PS)₂ and (η⁶-cymene)RuCl₂(PMePh₂). The complex Re(≡CCH₂Ph)(PS)₂ can be oxidized to give the sulfinate complex Re(≡CCH₂Ph)(H₂O)(PS_O)₂ (PS_O = Ph₂P-o-C₆H₄SO₂). The thiophenolate complexes Re(≡CR)(PMePh₂)(PS)₂ and Re(≡CR)(PS)₂ showed marginal alkyne metathesis activity at 100 °C, whereas the sulfinate complex Re(≡CCH₂Ph)(H₂O)(PS_O)₂ is unreactive toward alkyne metathesis reactions under similar condition. DFT calculations reveal that the lower metathesis activity of the thiophenolate and sulfinate complexes compared with that of PO complexes can be related to the thermochemistry of alkyne coordination to five-coordinated species Re(≡CR)(PX)₂ (X = O, S, S_O). The alkyne coordination to give an alkyne-alkylidyne complex is thermodynamically favored for Re(≡CR)(PO)₂, but is unfavored for Re(≡CR)(PS)₂ and Re(≡CR)(PS_O)_2, resulting in a higher barrier for alkyne metathesis in PS and PS_O systems.

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含ps螯合配体的碳炔铼配合物的合成及其炔烃复分解活性

受磷酚酸酯（PO）配体负载的Re(V)碳炔配合物催化炔复分解活性的启发，合成了具有类似磷硫杂化螯合配体的新型Re(V)碳炔配合物。Re(≡CR)Cl2(PMePh2)3 （R = CH2Ph, Ph）与（2-噻吩基）二苯基膦（Ph2P-o-C6H4SH， PSH）在NEt3存在下反应生成六配位PS配合物Re(≡CR)(PMePh2)(PS)2 (PS = Ph2P-o-C6H4S)，与[（η - 6-花枝烯）RuCl2]2反应生成五配位三角双锥体配合物Re(≡CR)(PS)2和（η - 6-花枝烯）RuCl2（PMePh2）。络合物Re(≡CCH2Ph)(PS)2可以被氧化生成亚硫酸盐络合物Re(≡CCH2Ph)(H2O)(PSO)2 （PSO = Ph2P-o-C6H4SO2）。噻吩酸盐配合物Re(≡CR)(PMePh2)(PS)2和Re(≡CR)(PS)2在100℃时表现出边际的炔还原反应活性，而亚硫酸盐配合物Re(≡CCH2Ph)(H2O)(PSO)2在相似条件下对炔还原反应无反应。DFT计算表明，硫代酚酸盐和亚硫酸盐配合物与PO配合物相比，其较低的复分解活性可能与炔与五配位物质Re(≡CR)(PX)2 （X = O， S， SO）的配位热化学有关。在热力学上，Re(≡CR)(PS)2和Re(≡CR)(PSO)2对炔配合物有利，但对Re(≡CR)(PS)2和Re(≡CR)(PSO)2不利，导致PS和PSO体系中炔复分解的势垒较高。

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来源期刊

European Journal of Inorganic Chemistry 化学-无机化学与核化学

CiteScore

4.30

自引率

4.30%

发文量

419

审稿时长

1.3 months

期刊介绍： The European Journal of Inorganic Chemistry (2019 ISI Impact Factor: 2.529) publishes Full Papers, Communications, and Minireviews from the entire spectrum of inorganic, organometallic, bioinorganic, and solid-state chemistry. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies. The following journals have been merged to form the two leading journals, European Journal of Inorganic Chemistry and European Journal of Organic Chemistry: Chemische Berichte Bulletin des Sociétés Chimiques Belges Bulletin de la Société Chimique de France Gazzetta Chimica Italiana Recueil des Travaux Chimiques des Pays-Bas Anales de Química Chimika Chronika Revista Portuguesa de Química ACH—Models in Chemistry Polish Journal of Chemistry The European Journal of Inorganic Chemistry continues to keep you up-to-date with important inorganic chemistry research results.