Chemistry inside a porphyrin skeleton: platinacyclopentadiene from tellurophene.

Platinum(II) binds to 21,23-ditelluraporphyrin forming a side-on complex, which can be easily transformed into an aromatic metallaporphyrin, i.e. 21-platina-23-telluraporphyrin, with a platinacyclopentadiene unit built in the porphyrin skeleton in place of one pyrrole ring. The central platinum(II) ion with CCNTe square planar coordination sphere can be oxidized to platinum(IV) by chlorine, bromine, methyl iodide or allyl chloride to yield octahedral complexes. All platinatelluraporphyrins show dynamic behavior involving the platinum ion coordination sphere fluxionality and the porphyrin skeleton deformation, both: in-plane and out-of-plane, as demonstrated by 1H NMR.

[1]  Edmundo G. Percástegui,et al.  Coordination-driven assemblies based on meso-substituted porphyrins: Metal-organic cages and a new type of meso-metallaporphyrin macrocycles , 2020 .

[2]  Justin K. Pagano,et al.  Actinide 2-metallabiphenylenes that satisfy Hückel’s rule , 2020, Nature.

[3]  J. Zink,et al.  Nanomachines and Other Caps on Mesoporous Silica Nanoparticles for Drug Delivery. , 2019, Accounts of chemical research.

[4]  F. Cortés‐Guzmán,et al.  Self-Assembly of Aluminum- and Gallium-Based meso-Metallaporphyrins. , 2019, Inorganic chemistry.

[5]  M. Ravikanth,et al.  Synthesis of Tellurabenziporphyrin and Its Pd(II) Complex. , 2018, Organic letters.

[6]  Z. Xi,et al.  The aromatic dianion metalloles , 2017, Chemical science.

[7]  T. Ema,et al.  Palladium Complexes of Carbazole-Based Chalcogenaisophlorins: Synthesis, Structure, and Solid-State NIR Absorption Spectra. , 2017, ChemPlusChem.

[8]  Vijayendra S. Shetti,et al.  Heteroatom-Containing Porphyrin Analogues. , 2017, Chemical reviews.

[9]  Tianyang Chen,et al.  Metallacyclopentadienes: synthesis, structure and reactivity. , 2017, Chemical Society reviews.

[10]  J. Lindsey,et al.  Synthetic Chlorins, Possible Surrogates for Chlorophylls, Prepared by Derivatization of Porphyrins. , 2017, Chemical reviews.

[11]  T. Lash.  Carbaporphyrinoid Systems. , 2017, Chemical reviews.

[12]  V. Anand,et al.  Controlled Core-Modification of a Porphyrin into an Antiaromatic Isophlorin. , 2016, Angewandte Chemie.

[13]  I. Bruno,et al.  Cambridge Structural Database , 2002 .

[14]  Michał J. Białek,et al.  Palladium(II), Ruthenium(II), and Ruthenium(III) Complexes of 23-Thiaazuliporphyrin: The Case of Coordination-Induced Contraction. , 2016, Inorganic chemistry.

[15]  V. Jain,et al.  New vistas in the chemistry of platinum group metals with tellurium ligands , 2016 .

[16]  B. E. Robertson,et al.  A comparative study of crystallographic van der Waals radii , 2014 .

[17]  L. Szterenberg,et al.  Gold(III)-mediated contraction of benzene to cyclopentadiene: from p-benziporphyrin to gold(III) true tetraarylcarbaporphyrin. , 2014, Chemistry.

[18]  L. Latos‐Grażyński,et al.  A porphyrin skeleton containing a palladacyclopentadiene. , 2013, Angewandte Chemie.

[19]  Y. Matano,et al.  Phosphole-containing calixpyrroles, calixphyrins, and porphyrins: synthesis and coordination chemistry. , 2009, Accounts of chemical research.

[20]  M. Kocik,et al.  Tetraazuliporphyrin tetracation. , 2009, Angewandte Chemie.

[21]  H. Nakano,et al.  Redox-coupled complexation of 23-phospha-21-thiaporphyrin with group 10 metals: a convenient access to stable core-modified isophlorin-metal complexes. , 2008, Journal of the American Chemical Society.

[22]  W. Price,et al.  195Pt NMR--theory and application. , 2007, Chemical Society reviews.

[23]  I. Butler,et al.  An Overview of 195Pt Nuclear Magnetic Resonance Spectroscopy , 2006 .

[24]  L. Latos‐Grażyński,et al.  Core modified porphyrins – a macrocyclic platform for organometallic chemistry , 2005 .

[25]  Miłosz Pawlicki,et al.  Iron complexes of 5,10,15,20-tetraphenyl-21-oxaporphyrin. , 2002, Inorganic chemistry.

[26]  M. Detty,et al.  21-Telluraporphyrins. 2. Catalysts for bromination reactions with hydrogen peroxide and sodium bromide , 2002 .

[27]  I. Guzei,et al.  Novel Coordination in the First Tellurium Porphyrin Complex: Synthesis and Crystal Structure of [Te(ttp)Cl2] , 2001 .

[28]  I. Guzei,et al.  Novel Coordination in the First Tellurium Porphyrin Complex: Synthesis and Crystal Structure of [Te(ttp)Cl(2)] This work was supported in part by the Research Corporation. ttp=meso-tetra-p-tolylporphyrin. , 2001, Angewandte Chemie.

[29]  Z. Ciunik,et al.  An Unorthodox Conformation of [18]porphyrin‐(1.1.1.1) Heteroanalogue—21,23‐Ditelluraporphyrin with a Flipped Tellurophene Ring , 2001 .

[30]  Z. Ciunik,et al.  An Unorthodox Conformation of [18]porphyrin-(1.1.1.1) Heteroanalogue-21,23-Ditelluraporphyrin with a Flipped Tellurophene Ring Financial support from the State Committee for Scientific Research KBN of Poland (Grant: 3 T09A 155 15) and the Foundation for Polish Science is gratefully acknowledged. , 2001, Angewandte Chemie.

[31]  S. Peng,et al.  Structure and characterization of the first metal complex of dithiaporphyrin: Ru(S(2)TTP)Cl(2). , 2001, Inorganic Chemistry.

[32]  A. Miralrio,et al.  Reactivity of Substituted Thiophenes toward Tris(triethylphosphine)platinum(0), -palladium(0), and -nickel(0) , 2001 .

[33]  R. J. Angelici.  Thiophenes in Organotransition Metal Chemistry: Patterns of Reactivity , 2001 .

[34]  A. Singh,et al.  Recent developments in the ligand chemistry of tellurium , 2000 .

[35]  T. Ogawa,et al.  N-Confused Tetraphenylporphyrin−Silver(III) Complex1 , 1999 .

[36]  A. G. Osborne,et al.  Synthesis and dynamic NMR studies of fluxionality in rhenium(I), platinum(II) and platinum(IV) complexes of ‘back-to-back’ 2,2′∶6′,2″-terpyridine ligands , 1998 .

[37]  A. G. Osborne,et al.  The energetics and mechanism of fluxionality of 2,2′∶6′,2″-terpyridine derivatives when acting as bidentate ligands in transition-metal complexes. A detailed dynamic NMR study , 1998 .

[38]  W. Jones,et al.  CARBON-SELENIUM BOND CLEAVAGE BY A RHODIUM COMPLEX , 1997 .

[39]  L. Latos‐Grażyński,et al.  EPR and 2H NMR Studies on the Oxidation of Nickel(II) Tetraphenylcarbaporphyrin To Form Novel Organometallic Nickel(III) Complexes , 1997 .

[40]  W. McWhinnie,et al.  Reactions of heterocyclic organotellurium compounds with triiron dodecacarbonyl: reactions of thiophenes revisited , 1996 .

[41]  A. Balch,et al.  Alteration of the Reactivity of a Tellurophene Within a Core‐Modified Porphyrin Environment: Synthesis and Oxidation of 21‐Telluraporphyrin , 1995 .

[42]  A. L. Balch,et al.  Änderung der Reaktivität eines Tellurophens durch eine Porphyrinumgebung: Synthese und Oxidation von 21-Telluraporphyrin† , 1995 .

[43]  L. Latos‐Grażyński,et al.  Low-valent nickel thiaporphyrins. Nuclear magnetic resonance and electron paramagnetic resonance studies , 1994 .