Synthesis,Crystal Structure of the Novel Rhodium（Ⅱ） Complex

doi:10.13438/j.cnki.jdzk.2023.04.007

Abstract

Abstract: Using rhodium（Ⅱ） acetate and trimethylrhodium acetate（Ⅱ） as the raw material,with 3,6-dibromo-9-(4-pyridinemethyl)-9H-carbazole (DBPMC1) and 3,6-dibromo-9-(3-pyridinemethyl)-9H-carbazole (DBPMC) as axial ligands,four rhodium（Ⅱ） carboxylates axial dibromo-9-pyridylmethyl-9H-carbazole complexes Rh(OOCR)4(DBPMC) were designed and synthesized.The single crystals of compounds were successfully cultured and their chemical structures were initially characterized by modern analytical methods such as H NMR,13C NMR and FT-IR.The results show that none of these four compounds has been reported in the literature,and they belong to a new type of rhodium carboxylate （Ⅱ） axial complex.The structure of the complex was determined by X-ray single crystal diffraction analysis to be composed of one molecule of rhodium（Ⅱ） carboxylate and two molecules of DBPMC ligand,and the molecular structure diagram and unit cell stacking diagram were drawn.

Key words: rhodium（Ⅱ） acetate, axial coordination, crystal structure, molecular structure diagram, cell stacking diagram

LIU Xue, TIAN Yiran, FENG Yangyang, XU Mingming, CHEN Honglai, HOU Wenming, ZHANG Zhenqiang, LIU Weiping. Synthesis,Crystal Structure of the Novel Rhodium（Ⅱ） Complex[J]. Journal of Jishou University(Natural Sciences Edition), 2023, 44(4): 55-68.

References

[1] COTTON F ALBERT,HILLARD ELIZABETH A,LIU CHUNY,et al.Steps on the Way to the First Dirhodium Tetracarboxylate with no Axial Ligation:Synthetic Lessons and a Plethora of Rh2(O2CR)4L2-n Compounds,n=0,1,2[J].Inorganica Chimica Acta,2002,337:233-246.
[2] MANG ANDR,LINSEIS MICHAEL,WINTER RAINER F.Synthesis and Crystal Structures of Rhodium Acetate Paddle-Wheel Complexes with Anchor Group-Functionalised and Hydrogen Bond-Supported Axial Ligands[J].Zeitschrift für anorganische und allgemeine Chemie,2022，648（23）：1-19.
[3] COTTON ALBERT F,DEBOER BARRY G,LAPRADE MARIE,et al.Multiple Chromium（Ⅱ）-Chromium（Ⅱ） and Rhodium（Ⅱ）-Rhodium（Ⅱ） Bonds[J].Journal of the American Chemical Society,2002,92(9):2926-2927.
[4] KITAMURA HIDEKI,OZAWA TOMOHIRO,JISUKAWA KOICHIRO,et al.Syntheses,Structures,and Properties of Tetrakis(μ-acetato)dirhodium（Ⅱ） Complexes with Axial Pyridine Nitrogen Donor Ligands with or Without Assistance of Hydrogen Bonds[J].Inorganic Chemistry,2000,39(15):3294-3300.
[5] XUE Wenmei,KHN FRITZ E.Tetranuclear Complexes Containing Bimetallic Tetracarboxylates and Ferrocene-Models for Subunits of One-Dimensional Organometallic Polymers[J].European Journal of Inorganic Chemistry,2001,2001(8):2041-2047.
[6] GTI TAMS,SIMON ANDRS,TTH GBOR,et al.Bis(phosphane oxide) Adducts of Rh2(MTPA)4-Kinetics and Chirality Discrimination[J].European Journal of Inorganic Chemistry,2004,10:2160-2166.
[7] JESSOP PHILIP G,OLMSTEAD MARILYN M,ABLAN CHRISTOPHER D,et al.Carbon Dioxide as a Solubility “Switch” for the Reversible Dissolution of Highly Fluorinated Complexes and Reagents in Organic Solvents:Application to Crystallization[J].Inorganic Chemistry,2002,41(13):3463-3468.
[8] FANDZLOCH MARZENA,AUGUSTYNIAK ADAM,DOBRZAN＇SKA LILIANA,et al.First Dinuclear Rhodium（Ⅱ） Complexes with Triazolopyrimidines and the Prospect of Their Potential Biological Use[J].Journal of Inorganic Biochemistry,2020,210:111072.DOI:10.1016/j.jinorgbio.2020.111072.
[9] ANDERSON BRADLEY G,CRESSY DEREK,PATEL JAY J,et al.Synthesis and Catalytic Properties of Dirhodium Paddlewheel Complexes with Tethered,Axially Coordinating Thioether Ligands[J].Inorganic Chemistry,2019,58(3):1728-1732.
[10] WARZRCHA EVAN,BERTO TIMOTHY C,BERR JOHN F.Axial Ligand Coordination to the C—H Amination Catalyst Rh2(esp)2:A Structural and Spectroscopic Study[J].Inorganic Chemistry,2015,54(17):8817-8824.
[11] TRINDADE ALEXANDRE F,COELHO JAIME A S,AFONSO CARLOS A M,et al.Fine Tuning of Dirhodium（Ⅱ） Complexes:Exploring the Axial Modification[J].ACS Catalysis,2012,2(3):370-383.
[12] BERRY JOHN F.The Role of Three-Center/Four-Electron Bonds in Superelectrophilic Dirhodium Carbene and Nitrene Catalytic Intermediates[J].Dalton Transactions,2012,41(3):700-713.
[13] YE Qingsong,LI Xiaonian,YI Jin,et al.Synthesis,Crystal Structures and Catalytic Activity of Tetrakis(acetato)dirhodium（Ⅱ） Complexes with Axial Picoline Ligands[J].Inorganica Chimica Acta,2015.434:113-120.
[14] REJ SUPRIYA,CHATANI NAOTO.Effect of Sulfonamide and Carboxamide Ligands on the Structural Diversity of Bimetallic RhII-RhII Cores:Exploring the Catalytic Activity of These Newly Synthesized Rh2 Complexes[J].Inorganic Chemistry,2021,60(6):3534-3538.
[15] HONG Biqiong,SHI Lei,LI Lin,et al.Paddlewheel Dirhodium（Ⅱ） Complexes with N-Heterocyclic Carbene or Phosphine Ligand:New Reactivity and Selectivity[J].Green Synthesis and Catalysis,2022,3(2):137-149.
[16] XUE Wenmei,KHN FRITZ E,HERDTWECK EBERHARDT,et al.Organometallic Polymers with the Backbone Consisting of Ferrocene and Bimetallic Tetracarboxylates[J].European Journal of Inorganic Chemistry,2001,2001(1):213-221.
[17] 余娟,刘俊,巨少英,等.碳酸二羟基·四氨合铂(Ⅳ)二水合物的合成、表征及性质[J].贵金属,2019,40(4):1-6.
[18] 侯文明,崔浩,叶青松,等.醋酸铑（Ⅱ）与2-吡啶羧酸的反应研究[J].贵金属,2017,38(S1):127-133.