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1. Synthetic Approaches to and Structures of Diplatinum Polyynediyl Complexes trans,trans ‐[(C ₆ F ₅ )(R ₃ P) ₂ Pt(C≡C) _n Pt(PR ₃ ) ₂ (C ₆ F ₅ )] With Odd Numbers of Triple Bonds; Avoiding Complicating Ethynediyl Extrusions

   https://doi.org/10.1002/ejic.202400428  

   Dey_Baksi, Sourajit; Weisbach, Nancy; Bhuvanesh, Nattamai; Gladysz, John_A (October 2024, European Journal of Inorganic Chemistry)

   Abstract Reactions oftrans‐(C₆F₅)(p‐tol₃P)₂Pt(C≡C)_nSiEt₃(PtC_2nSi;n=5, 7, 9) and excessPtClin the presence of wetn‐Bu₄N⁺F⁻(to effect protodesilylation) under Sonogashira‐type conditions (CuCl, base, other additives) afford the title compoundsPtC₁₀Pt,PtC₁₄Pt, andPtC₁₈Ptin 42–32 % yields. A four‐fold substitution of the phosphine ligands inPtC₁₀Ptby PEt₃affordsPt'C₁₀Pt’(78 %), and a Sonogashira reaction ofPt'C₂HandPt'ClaffordsPt'C₂Pt’(68 %). The analogous reaction withPtC₂SiandPtClis unsuccessful, presumably for steric reasons. The crystal structures ofPtC₁₀Pt,PtC₁₄Pt,Pt'C₁₀Pt′, andPt'C₂Pt’exhibit a number of interesting trends and features. Certain sp chain extension reactions that lead to or employ the precursorsPtC₁₀Si,PtC₁₂Si,PtC₁₄Si, andPtC₁₈Sisometimes give byproducts derived from C₂loss, and possible origins are discussed. Related phenomena have been reported by others in the course of synthesizing extended conjugated polyynes. 

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2. “Click” Chemistry in Metal Coordination Spheres: Copper(I)-Catalyzed 3+2 Cycloadditions of Benzyl Azide and Platinum Polyynyl Complexes trans -(C ₆ F ₅ )( p -tol ₃ P) ₂ Pt(C≡C) _n H ( n = 2−6)

   https://doi.org/10.1021/om900680q  

   Gauthier, Sébastien; Weisbach, Nancy; Bhuvanesh, Nattamai; Gladysz, John A. (October 2009, Organometallics)
3. Controlling Stoichiometry in Ultrathin van der Waals Films: PtTe ₂ , Pt ₂ Te ₃ , Pt ₃ Te ₄ , and Pt ₂ Te ₂

   https://doi.org/10.1021/acsnano.2c04303  

   Lasek, Kinga; Ghorbani-Asl, Mahdi; Pathirage, Vimukthi; Krasheninnikov, Arkady V.; Batzill, Matthias (June 2022, ACS Nano)
4. sp Carbon Chains Surrounded by sp ³ Carbon Double Helices:  Coordination-Driven Self-Assembly of Wirelike Pt(C⋮C) _n Pt Moieties That Are Spanned by Two P(CH ₂ ) _m P Linkages

   https://doi.org/10.1021/ja0716103  

   Stahl, Jürgen; Mohr, Wolfgang; de Quadras, Laura; Peters, Thomas B.; Bohling, James C.; Martín-Alvarez, José Miguel; Owen, Gareth R.; Hampel, Frank; Gladysz, John A. (July 2007, Journal of the American Chemical Society)
5. Platinum Elimination from Bis(triethylsilylpolyynyl) Complexes ( n ‐Bu ₂ C(CH ₂ PPh ₂ ) ₂ )Pt((C≡C) _n SiEt ₃ ) ₂ ( n =2, 3) and Macrocycles Comprised of Four L ₂ Pt Corners and Four C≡CC≡CC≡C Linkers; An Approach to Cyclo[24]carbon

   https://doi.org/10.1002/chem.202402833  

   Collins, Brenna_K; Gladysz, John_A (October 2024, Chemistry – A European Journal)

   Abstract The overarching goal of this study is to effect the elimination of platinum from adducts withcis–C≡C−Pt−C≡C‐ linkages, thereby generating novel conjugated polyynes. Thus, the bis(hexatriynyl) complextrans‐(p‐tol₃P)₂Pt((C≡C)₃H)₂is treated with 1,3‐diphosphines R₂C(CH₂PPh₂)₂to generate (R₂C(CH₂PPh₂)₂)₂Pt((C≡C)₃H)₂(14; R=c,n‐Bu;e,p‐tolCH₂). These condense with the diiodide complexes R₂C(CH₂PPh₂)₂PtI₂(9 a,c) in the presence of CuI (cat.) and excess HNEt₂to give the title macrocycles [(R₂C(CH₂PPh₂)₂)Pt(C≡C)₃]₄(16 c,e) as adducts of the byproduct [H₂NEt₂]⁺I⁻(30–66 %). DOSY NMR experiments establish that this association is maintained in solution, but NaOAc removes the ammonium salt. The bis(triethylsilylpolyynyl) complexes (n‐Bu₂C(CH₂PPh₂)₂)Pt((C≡C)_nSiEt₃)₂(n=2, 3) are synthesized analogously to14 c. They react with I₂at rt to give mainly the diiodide complex9 cand the coupling product Et₃Si(C≡CC≡C)_nSiEt₃. The possibility of competing reactions giving IC≡C species is investigated. Analogous reactions of the Pt₄C₂₄macrocycle16 calso give9 c, but no sp¹³C NMR signals or mass spectrometric C_x^z+ions (x=24–100) could be detected. It is proposed that some cyclo[24]carbon is generated, but then rapidly converts to other forms of elemental carbon. No cyclotetracosane (C₂₄H₄₈) is detected when this sequence is carried out in the presence of PtO₂and H₂. 

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