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1. Synthesis, Reactivity, and Metal Complexes of Fluorous Triarylphosphines of the Formula P( p- C 6 H 4 (CH 2 ) 3 (CF 2 ) n - 1 CF 3 ) 3 ( n = 6, 8, 10)

   https://doi.org/10.1021/om010193e  

   Soós, Tibor ; Bennett, Byron L. ; Rutherford, Drew ; Barthel-Rosa, Luis P. ; Gladysz, J. A. ( July 2001 , Organometallics)
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. Platinum( ii ) alkyl complexes of chelating dibridgehead diphosphines P((CH 2 ) n ) 3 P ( n = 14, 18, 22); facile cis / trans isomerizations interconverting gyroscope and parachute like adducts

   https://doi.org/10.1039/D1DT02321G  

   Zhu, Yun ; Ehnbom, Andreas ; Fiedler, Tobias ; Shu, Yi ; Bhuvanesh, Nattamai ; Hall, Michael B. ; Gladysz, John A. ( September 2021 , Dalton Transactions)

   The gyroscope like dichloride complexes trans -Pt(Cl) 2 (P((CH 2 ) n ) 3 P) ( trans -2; n = c, 14; e, 18; g, 22) and MeLi (2 equiv.) react to yield the parachute like dimethyl complexes cis -Pt(Me) 2 (P((CH 2 ) n ) 3 P) ( cis -4c,e,g, 70–91%). HCl (1 equiv.) and cis -4c react to give cis -Pt(Cl)(Me)(P((CH 2 ) 14 ) 3 P) ( cis -5c, 83%), which upon stirring with silica gel or crystallization affords trans -5c (89%). Similar reactions of HCl and cis -4e,g give cis / trans -5e,g mixtures that upon stirring with silica gel yield trans -5e,g. A parallel sequence with trans -2c/EtLi gives cis -Pt(Et) 2 (P((CH 2 ) 14 ) 3 P) ( cis -6c, 85%) but subsequent reaction with HCl affords trans -Pt(Cl)(Et)(P((CH 2 ) 14 ) 3 P) ( trans -7c, 45%) directly. When previously reported cis -Pt(Ph) 2 (P((CH 2 ) 14 ) 3 P) is treated with HCl (1 equiv.), cis - and trans -Pt(Cl)(Ph)(P((CH 2 ) 14 ) 3 P) are isolated (44%, 29%), with the former converting to the latter at 100 °C. Reactions of trans -5c and LiBr or NaI afford the halide complexes trans -Pt(X)(Me)(P((CH 2 ) 14 ) 3 P) ( trans -9c, 88%; trans -10c, 87%). Thermolyses and DFT calculations that include acyclic model compounds establish trans > cis stabilities for all except the dialkyl complexes, for which energies can be closely spaced. The σ donor strengths of the non-phosphine ligands are assigned key roles in the trends. The crystal structures of cis -4c, trans -5c, trans -7c, and trans -10c are determined and analyzed together with the computed structures. 

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4. Syntheses, Structures, and Thermal Properties of Gyroscope-like Complexes Consisting of PtCl 2 Rotators Encased in Macrocyclic Dibridgehead Diphosphines P((CH 2 ) n ) 3 P with Extended Methylene Chains ( n = 20/22/30) and Isomers Thereof

   https://doi.org/10.1021/acs.organomet.8b00345  

   Kharel, Sugam ; Joshi, Hemant ; Bhuvanesh, Nattamai ; Gladysz, John A. ( September 2018 , Organometallics)
5. Molecules that Turn Themselves Inside‐Out: Tuning in / out Equilibria and Homeomorphic Isomerization in Macrobicyclic Dibridgehead Diphosphines P((CH 2 ) n ) 3 P Newly Accessible by Earth‐Abundant‐Metal Templates

   https://doi.org/10.1002/chem.202302200  

   Zarcone, Samuel R. ; Bhuvanesh, Nattamai ; Gladysz, John A. ( November 2023 , Chemistry – A European Journal)

   Photolyses oftrans‐Fe(CO)₃(P((CH₂)_n)₃P) (n=10 (a), 12 (b), 14 (c), 16 (d), 18 (e)) in the presence of PMe₃provide the first economical and scalable route to macrobicyclic dibridgehead diphosphines P((CH₂)_n)₃P (1). These are isolated as mixtures ofin,in/out,outisomers that equilibrate with degeneratein,out/out,inisomers at 150 °C via pyramidal inversion at phosphorus. For the entire series, VT³¹P NMR data establish or boundK_eq, rates, and activation parameters for a variety of phenomena, many of which involve homeomorphic isomerizations, topological processes by which certain molecules can turn themselves inside out (e. g.,in,in⇌out,out). This provides the first detailed mapping of such trends in homologous series of aliphatic bicyclic compounds XE((CH₂)_n)₃EX with any type of bridgehead. Isomeric diborane adducts1 a,d ⋅ 2BH₃are also characterized. Crystal structures ofout,out‐1 aandin,in‐1 a ⋅ 2BH₃aid isomer assignments and reveal unusual cage conformations.

    

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