Organometallics最新文献

{"title":"Methyl-Branched Polyethylene Produced by Hafnocene Complexes Exhibiting Unconventional Dialkoxy Bridges","authors":"Tim M. Lenz,&nbsp;Juliana Steck,&nbsp;Jin Y. Liu and Bernhard Rieger*,&nbsp;","doi":"10.1021/acs.organomet.4c0045910.1021/acs.organomet.4c00459","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00459https://doi.org/10.1021/acs.organomet.4c00459","url":null,"abstract":"<p >Research on the homogeneous polymerization of propylene employing group IV metallocene complexes primarily focuses on structures like <i>rac</i>-dimethylsilanediylbis(4-phenyl-7-methoxy-2-methylindenyl)hafnium dichloride (<i>rac</i>-<b>I</b>), featuring the long-established <i>Spaleck</i>-type −SiMe₂– bridge between two indenyl fragments, while such complexes are rarely used in ethylene polymerization. This work describes the syntheses and polymerization performances of two hafnocene complexes, <i>rac</i>-ethane-1,2-diyl((2-methyl-7-phenyl-1<i>H</i>-inden-4-yl)oxy)hafnium dichloride (<i>rac</i>-<b>II</b>) and <i>rac</i>-propane-1,3-diyl((2-methyl-7-phenyl-1<i>H</i>-inden-4-yl)oxy)hafnium dichloride (<i>rac</i>-<b>III</b>), bearing unconventional dialkoxy bridges of varying lengths. Single-crystal X-ray diffraction experiments enabled the comparison of characteristic geometric parameters between the two synthesized hafnocenes and <i>Spaleck</i>-type complex <i>rac</i>-<b>I</b>. Upon activation with different cocatalysts, <i>rac</i>-<b>II</b> and <i>rac</i>-<b>III</b> yielded polyethylene with exclusively methyl branches, contrary to long-chain branches, which are usually formed when group IV metallocene complexes are applied for ethylene polymerization. Thus, a branching mechanism related to the prominent chain-walking mechanism, which is frequently observed for late transition-metal complexes, is proposed. Furthermore, the degree of branching could be regulated by adjusting the employed cocatalysts, polymerization temperatures, and bridge lengths, allowing the control of the polymers’ melting transition temperatures.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 1","pages":"8–13 8–13"},"PeriodicalIF":2.5,"publicationDate":"2024-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.4c00459","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143087050","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Zirconium Complex Bearing an [NPN] Tridentate Ligand Composed of Dibenzophosphole and Pyrrolide Moieties: Synthesis, Structure, and Ethylene-Polymerization Ability","authors":"Tomoyuki Toda*,&nbsp;Yuzuki Kasahara,&nbsp;Jin Iwasaki,&nbsp;Ayana Wakatsuki,&nbsp;Shun Ohta,&nbsp;Yoshihiro Matano and Katsuhiko Takenaka,&nbsp;","doi":"10.1021/acs.organomet.4c0039510.1021/acs.organomet.4c00395","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00395https://doi.org/10.1021/acs.organomet.4c00395","url":null,"abstract":"<p >Post-metallocene catalysts constitute a remarkable class of homogeneous olefin polymerization catalysts owing to their exceptional activity and unique ability to copolymerize ethylene with α-olefins. The synthesis of Group 4 metal complexes, adorned with unprecedented ligand frameworks, has immense potential to yield polymerization performance surpassing that of conventional catalysts. In this field, soft/hard-mix-donor-type ligands have recently emerged as a focal point in the design of novel ligands for Group 4 transition metals. Thus, we herein synthesized an [NPN]-tridentate dianionic ligand containing dibenzophosphole and pyrrolides as a new type of soft/hard base mix-donor-type ligand and its zirconium complex, denoted as [NPN]Zr(NEt₂)₂. The [NPN] ligand and [NPN]Zr(NEt₂)₂ were comprehensively characterized by NMR and single-crystal X-ray crystal analysis. Ethylene homopolymerization was conducted under various conditions to determine the polymerization activity of [NPN]Zr(NEt₂)₂. In particular, ethylene polymerization was conducted at 0.1 MPa and 30 °C and catalyzed with [NPN]Zr(NEt₂)₂ with dried modified methylalumoxane as an activator, resulting in 7600 kg of (PE) mol(Zr)⁻¹ h^–1 MPa^–1 activity and linear PE with a high melting point. Overall, this study expands the repertoire of Group 4 metal catalysts, while underscoring their proficiency in tailoring advanced polymeric materials.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 1","pages":"128–136 128–136"},"PeriodicalIF":2.5,"publicationDate":"2024-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143086974","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Impact of Halide (Cl vs I) Identity on the Preferred Positioning of Substituents between Al and M (M = Co, Rh, Ir) in PAlP Pincer Complexes.","authors":"Samuel R Lee, Natchayatorn Keawkla, R Noah Sladek, Nattamai Bhuvanesh, Panida Surawatanawong, Oleg V Ozerov","doi":"10.1021/acs.organomet.4c00490","DOIUrl":"10.1021/acs.organomet.4c00490","url":null,"abstract":"<p><p>Protolysis of AlMe₃ or AlEt₃ with 2-diisopropylphosphinopyrrole (<b>1</b>) resulted in alane/bis(phosphine) pincer ligands containing two flanking phosphines and a central Al-Me (<b>2-Me</b>), Al-Et (<b>2-Et</b>) unit. Reactions of <b>2-Me</b> with [(COD)MI]₂ (COD = 1,5-cyclooctadiene; M = Rh or Ir) in the presence of pyridine produced pincer complexes (<b>3-Rh-I</b> and <b>3-Ir-I</b>) with M supported by the PAlP tridentate ligand, and pyridine, methyl, and iodide as monodentate ligands for Al or M. The analogous reaction of <b>2-Et</b> with [(COD)MI]₂ and pyridine resulted in the formation of the analogous compounds <b>4-Rh-I</b> and <b>4-Ir-I</b> with hydride in place of methyl. DFT calculations were used to analyze the thermodynamic preferences for the positioning of pyridine, methyl or hydride, and the halide (chloride or iodide) on M vs Al. Cobalt was included with Rh and Ir among M for the purposes of DFT calculations. Theoretical studies suggested that different isomers are preferred for the iodide complexes (M-I and Al-Py) than for the chloride ones (M-py and Al-Cl, previously reported for Rh and Ir). X-ray structural study of <b>3-Rh-I</b> and analysis of the ¹H NMR data of the Rh and Ir compounds in benzene corroborated these predictions.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 1","pages":"347-353"},"PeriodicalIF":2.5,"publicationDate":"2024-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11734121/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996256","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Impact of Halide (Cl vs I) Identity on the Preferred Positioning of Substituents between Al and M (M = Co, Rh, Ir) in PAlP Pincer Complexes","authors":"Samuel R. Lee,&nbsp;Natchayatorn Keawkla,&nbsp;R. Noah Sladek,&nbsp;Nattamai Bhuvanesh,&nbsp;Panida Surawatanawong* and Oleg V. Ozerov*,&nbsp;","doi":"10.1021/acs.organomet.4c0049010.1021/acs.organomet.4c00490","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00490https://doi.org/10.1021/acs.organomet.4c00490","url":null,"abstract":"<p >Protolysis of AlMe₃ or AlEt₃ with 2-diisopropylphosphinopyrrole (<b>1</b>) resulted in alane/bis(phosphine) pincer ligands containing two flanking phosphines and a central Al–Me (<b>2-Me</b>), Al–Et (<b>2-Et</b>) unit. Reactions of <b>2-Me</b> with [(COD)MI]₂ (COD = 1,5-cyclooctadiene; M = Rh or Ir) in the presence of pyridine produced pincer complexes (<b>3–Rh–I</b> and <b>3–Ir–I</b>) with M supported by the PAlP tridentate ligand, and pyridine, methyl, and iodide as monodentate ligands for Al or M. The analogous reaction of <b>2-Et</b> with [(COD)MI]₂ and pyridine resulted in the formation of the analogous compounds <b>4–Rh–I</b> and <b>4–Ir–I</b> with hydride in place of methyl. DFT calculations were used to analyze the thermodynamic preferences for the positioning of pyridine, methyl or hydride, and the halide (chloride or iodide) on M vs Al. Cobalt was included with Rh and Ir among M for the purposes of DFT calculations. Theoretical studies suggested that different isomers are preferred for the iodide complexes (M–I and Al–Py) than for the chloride ones (M–py and Al–Cl, previously reported for Rh and Ir). X-ray structural study of <b>3–Rh–I</b> and analysis of the ¹H NMR data of the Rh and Ir compounds in benzene corroborated these predictions.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 1","pages":"347–353 347–353"},"PeriodicalIF":2.5,"publicationDate":"2024-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.4c00490","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143087238","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis and Characterization of a 1,2,4-Diazarsolide Anion.","authors":"William D Jobbins, Bono van IJzendoorn, Meera Mehta","doi":"10.1021/acs.organomet.4c00476","DOIUrl":"10.1021/acs.organomet.4c00476","url":null,"abstract":"<p><p>Cyclopentadienyl anions ([Cp]^-) are pervasive ligands in coordination chemistry. In contrast, heavy-element derivatives of these ligands, particularly those that feature arsenic, are not as well developed. In this work, a new arsenic-based heterocycle with a structure analogous to [Cp]^- is presented. Reaction of K₃As₇ with benzyl azide (BnN₃) leads to fragmentation of the [As₇]^3- core and C-H activation of two [BnN] units to give the five-membered arsenic heterocycle [As(NC(Ph))₂]^-. This arsenic heterocycle was studied by nuclear magnetic resonance and UV-vis spectroscopy, X-ray diffraction, and its electronic structure was investigated computationally.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 1","pages":"14-18"},"PeriodicalIF":2.5,"publicationDate":"2024-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11734114/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996258","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Chromium(II)/(III) Complexes Bearing Phosphino-N-Heterocyclic Carbene and N-Chelating N-Heterocyclic Carbene Ligands and Their Use in Ethylene Oligomerization","authors":"Somnath Bhattacharya,&nbsp;Boshra Atwi,&nbsp;Koushani Kundu,&nbsp;Wolfgang Frey and Michael R. Buchmeiser*,&nbsp;","doi":"10.1021/acs.organomet.4c0045810.1021/acs.organomet.4c00458","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00458https://doi.org/10.1021/acs.organomet.4c00458","url":null,"abstract":"<p >The bidentate Cr(III) phosphino-<i>N</i>-heterocyclic carbene (NHC) complex [(1-(2,6-diisopropylphen-1-yl)-3-(1-diphenylphosphinoeth-2-ylimidazol-2-ylidene)CrCl₃(THF)] (<b>Cr1</b>) as well as the Cr(II) and Cr(III) complexes [(1-methyl-3-(2-amido-<i>N</i>-(2,6-diisopropylpheny-1-yl)phen-1-ylimidazol-2-ylidene)₂Cr₂-(μ-Cl)₄] (<b>Cr2</b>), [(1-methyl-3-(2-amido-<i>N</i>-(2-biphen-1-yl)phen-1-ylimidazol-2-ylidene)₂Cr₂-(μ-Cl)₄] (<b>Cr3</b>), [(1-methyl-3-(2-amido-<i>N</i>-(2,6-diisopropylpheny-1-yl)phen-1-ylimidazol-2-ylidene)₂Cr₂-(μ-Cl)₄] (<b>Cr4</b>), [(1-methyl-3-(2-amido-<i>N</i>-(2,6-diisopropylpheny-1-yl)phen-1-ylimidazol-2-ylidene)Cr(benzyl)₂(THF)] (<b>Cr5</b>), [(1-methyl-3-(2-amido-<i>N</i>-(2,6-diisopropylpheny-1-yl)phen-1-ylimidazol-2-ylidene)₂Cr] (<b>Cr7</b>), [(1-methyl-3-(2-amido-<i>N</i>-(2,6-diisopropylpheny-1-yl)phen-1-ylimidazol-2-ylidene)₂Cr₂-(μ-Cl)₂(Cl)₂(THF)₂] (<b>Cr8</b>), [(1-methyl-3-(2-amido-<i>N</i>-(2-biphen-1-yl)phen-1-ylimidazol-2-ylidene)₂Cr] (<b>Cr10</b>), [(1-methyl-3-(2-amido-<i>N</i>-(2-biphen-1-yl)phen-1-ylimidazol-2-ylidene)Cr-(μ-Cl)₂(1-methyl-3-(2-amido-<i>N</i>-(2-biphen-1-yl)phen-1-ylimidazol-2-ylidene)₂Cr] (<b>Cr11</b>) containing a bidentate <i>N</i>-chelating NHC, as well as the Cr(II) cyclic alkylamino carbene (CAAC) complex [(CAAC)₂CrCl₂] (<b>Cr6</b>, CAAC = 1-(2,6-diisopropylpheny-1-yl)-3,3,5,5-tetramethyltetrahydropyrrol-2-ylidene) have been prepared. <b>Cr1</b>, <b>Cr4</b>, <b>Cr7</b>, <b>Cr8</b>, and <b>Cr10</b>–<b>Cr12</b> were characterized by single-crystal X-ray analysis. The molecular structure of <b>Cr4</b> features a binuclear complex comprising two Cr(II) metal centers where each metal center adopts a distorted square planar geometry, whereas <b>Cr11</b> represents a noteworthy addition to the rare class of structurally characterized mixed-valence Cr-complexes composed of two nonequivalent Cr centers with formal Cr(II) and Cr(III) oxidation states. In the presence of methylalumoxane (MAO) as a cocatalyst, the novel chromium complexes display catalytic activity in ethylene oligomerization. Complex <b>Cr2</b>, with an <i>N</i>-diisopropylphenyl group, shows ca. 7 times higher polymerization activity (8.1 kg mol Cr^–1 h^–1 bar^–1) than <b>Cr3</b> (1.1 kg mol Cr^–1 h^–1 bar^–1) bearing a bulky, yet flexible <i>N</i>-biphen-1-ylamine unit, indicating that less bulky ligands can enhance catalytic activity in chelated Cr complexes. The Cr(II)-CAAC complex <b>Cr6</b> possesses increased activity compared to a structurally similar Cr(II)-NHC complex.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 1","pages":"315–324 315–324"},"PeriodicalIF":2.5,"publicationDate":"2024-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143087146","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis and Characterization of a 1,2,4-Diazarsolide Anion","authors":"William D. Jobbins,&nbsp;Bono van IJzendoorn and Meera Mehta*,&nbsp;","doi":"10.1021/acs.organomet.4c0047610.1021/acs.organomet.4c00476","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00476https://doi.org/10.1021/acs.organomet.4c00476","url":null,"abstract":"<p >Cyclopentadienyl anions ([Cp]⁻) are pervasive ligands in coordination chemistry. In contrast, heavy-element derivatives of these ligands, particularly those that feature arsenic, are not as well developed. In this work, a new arsenic-based heterocycle with a structure analogous to [Cp]⁻ is presented. Reaction of K₃As₇ with benzyl azide (BnN₃) leads to fragmentation of the [As₇]^3– core and C–H activation of two [BnN] units to give the five-membered arsenic heterocycle [As(NC(Ph))₂]⁻. This arsenic heterocycle was studied by nuclear magnetic resonance and UV–vis spectroscopy, X-ray diffraction, and its electronic structure was investigated computationally.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 1","pages":"14–18 14–18"},"PeriodicalIF":2.5,"publicationDate":"2024-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.4c00476","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143087163","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Rhodium-Promoted anti-Hydroboration of Terminal Alkynes via Combined Stoichiometric Reactions","authors":"Laura A. de las Heras,&nbsp;Miguel A. Esteruelas*,&nbsp;Katarzyna A. Mituła-Chmielowiec,&nbsp;Montserrat Oliván and Enrique Oñate,&nbsp;","doi":"10.1021/acs.organomet.4c0039310.1021/acs.organomet.4c00393","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00393https://doi.org/10.1021/acs.organomet.4c00393","url":null,"abstract":"<p >Reactions of RhH{κ³-<i>P,O,P</i>-[xant(PⁱPr₂)₂]} (xant(PⁱPr₂)₂ = 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene) with 2 equiv of <i>tert</i>-butylacetylene and phenylacetylene lead to the acetylide derivatives Rh(C≡CR){κ³-<i>P,O,P</i>-[xant(PⁱPr₂)₂]} (R = ^tBu, Ph). The C–C triple bond of these compounds undergoes the B–H <i>anti</i>-addition of pinacolborane (HBpin) to produce Rh{(<i>E</i>)-C(Bpin)=CHR-<i>Pro-Z</i>}{κ³-<i>P,O,P</i>-[xant(PⁱPr₂)₂]} (R = ^tBu, Ph), which regenerate Rh(C≡CR){κ³-<i>P,O,P</i>-[xant(PⁱPr₂)₂]} in the presence of a new alkyne molecule, releasing the respective (<i>Z</i>)-borylolefin. Complex Rh{(<i>E</i>)-C(Bpin)=CHPh-<i>Pro-Z</i>}{κ³-<i>P,O,P</i>-[xant(PⁱPr₂)₂]} is unstable in toluene. Initially, the C–C double bond of the borylalkenyl ligand undergoes a <i>E</i> to <i>Z</i> isomerization to produce Rh{(<i>Z</i>)-C(Bpin)═CHPh-<i>Pro-E</i>}{κ³-<i>P,O,P</i>-[xant(PⁱPr₂)₂]}, which subsequently evolves to the aryl derivative Rh{C₆H₄-2-[<i>E</i>-CH═CH(Bpin)]}{κ³-<i>P,O,P</i>-[xant(PⁱPr₂)₂]}. The latter reacts with a new phenylacetylene molecule to produce Rh(C≡CPh){κ³-<i>P,O,P</i>-[xant(PⁱPr₂)₂]} and the (<i>E</i>)-borylolefin. According to this reactivity, the complex RhH{κ³-<i>P,O,P</i>-[xant(PⁱPr₂)₂]} is an effective catalyst precursor for the hydroboration of terminal alkynes to mixtures of (<i>Z</i>)- and (<i>E</i>)-borylolefins. The molar ratio between isomers depends on the substituent of the alkyne; <i>para</i>-substituted aryl substituents with electron-withdrawing groups favor <i>Z</i>-borylolefin.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 1","pages":"115–127 115–127"},"PeriodicalIF":2.5,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143086663","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Computational Prediction and Experimental Confirmation of the Reaction between 1-Lithio-1,3-Butadiene and White Phosphorus Affording Phospholyl Lithium","authors":"Yaqi Zhao,&nbsp;Zhengqi Chai,&nbsp;Zhiyi Song,&nbsp;Junnian Wei and Wen-Xiong Zhang*,&nbsp;","doi":"10.1021/acs.organomet.4c0045110.1021/acs.organomet.4c00451","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00451https://doi.org/10.1021/acs.organomet.4c00451","url":null,"abstract":"<p >The direct construction of C–P bonds from white phosphorus (P₄) and nucleophilic reagents is of great scientific importance and application value. In this work, density functional theory calculations reveal the reaction mechanism of P₄ with the <i>mono</i>-lithium reagent, namely, 1,2,3,4-tetraethyl-1-lithiobuta-1,3-diene. The construction of C–P bonds is realized through the sequential nucleophilic attacks of the C–Li bond toward P₄ and P–P bonds toward the butadiene skeleton. The calculation results were confirmed by the model reaction of 1,2,3,4-tetraethyl-1-lithiobuta-1,3-diene with P₄ providing the corresponding phospholyl lithium selectively. This work combining computational prediction with experimental confirmation opens a new avenue for the discovery of the selective reaction between <i>mono</i>-lithium reagents and white phosphorus.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 1","pages":"300–306 300–306"},"PeriodicalIF":2.5,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143086207","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis of [Fe2[(μ-SeCH2)2NH](CN)2(CO)4]2– and Related Iron Selenoates","authors":"Xin Yu,&nbsp;Toby J. Woods and Thomas B. Rauchfuss*,&nbsp;","doi":"10.1021/acs.organomet.4c0045710.1021/acs.organomet.4c00457","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00457https://doi.org/10.1021/acs.organomet.4c00457","url":null,"abstract":"<p >The dianion [Fe₂[(μ-SeCH₂)₂NH](CN)₂(CO)₄]^2– ([<b>2</b>]^2–) is of interest for the preparation of the selenide analog of the active site of the [FeFe]-hydrogenases. The obvious route for its synthesis by cyanation of Fe₂[(μ-SeCH₂)₂NH](CO)₆ (<b>3</b>) fails for reasons that this paper explains and resolves. We show that CN^– cleaves Se–C bonds in <b>3</b>. For example, treatment of Fe₂[(μ-SeCH₂)₂NH](CO)₆ with NEt₄CN followed by CH₃I gives substantial amounts of Fe₂(μ-SeCH₃)₂(CO)₆. Authentic [<b>2</b>]^2– can be obtained by cyanation of Fe₂[(μ-SeCH₂)₂NH](CO)₅(pyridine). The ⁷⁷Se NMR data for [<b>2</b>]^2– and <b>3</b> are reevaluated and explained. Attempts to prepare Fe₂[(μ-SeCH₂)₂NH](PPh₃)₂(CO)₄ (<b>9</b>) by Me₃NO-induced decarbonylation of <b>3</b> also suffers from degradation of the organoselenium ligand. Complex <b>9</b> was prepared instead by photosubstitution. The protonation of [<b>2</b>]^2– and [Fe₂[(μ-SCH₂)₂NH](CN)₂(CO)₄]^2– are compared: the selenium compounds are more basic. The structure of [HFe₂[(μ-SCH₂)₂NH](CN)₂(CO)₄]⁻ was determined crystallographically.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 1","pages":"307–314 307–314"},"PeriodicalIF":2.5,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.4c00457","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143085662","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}