Macrocyclic Metal Complexes Bearing Rigid Polyaromatic Ligands: Synthesis and Catalytic Activity.

We synthesised palladium and platinum complexes possessing cyclic and acyclic pincer-type polyaromatic ligands and investigated their structural effect on the catalysis. The pincer-type bis(6-arylpyridin-2-yl)benzene skeleton was constructed via Kröhnke pyridine synthesis under transition metal-free conditions at gram-scale quantity. Ligand structure significantly influenced catalytic activity toward the platinum-catalysed hydrosilylation of diphenyl acetylenes, despite the ligand-independence of these complexes' conformations and electronic properties.

[1]  Adrian B. Chaplin,et al.  Rhodium(III) and Iridium(III) Complexes of a NHC-Based Macrocycle: Persistent Weak Agostic Interactions and Reactions with Dihydrogen , 2018, Organometallics.

[2]  Adrian B. Chaplin,et al.  Terminal Alkyne Coupling Reactions through a Ring: Mechanistic Insights and Regiochemical Switching , 2018, Angewandte Chemie.

[3]  T. Takata,et al.  Chemoselective Suzuki Coupling of Bromoarenes Catalysed by Palladium(II)‐Complexing Macrocycles in Aqueous Media , 2018 .

[4]  Akshai Kumar,et al.  Dehydrogenation of Alkanes and Aliphatic Groups by Pincer-Ligated Metal Complexes. , 2017, Chemical reviews.

[5]  Nicola H. Green,et al.  Oxygen Mapping of Melanoma Spheroids using Small Molecule Platinum Probe and Phosphorescence Lifetime Imaging Microscopy , 2017, Scientific Reports.

[6]  Hiromi Ota,et al.  Chiral Macrocyclic Organocatalysts for Kinetic Resolution of Disubstituted Epoxides with Carbon Dioxide. , 2017, Organic letters.

[7]  T. Kanbara,et al.  Modulation of the Emission Mode of a Pt(II) Complex via Intermolecular Interactions. , 2017, Inorganic chemistry.

[8]  Jye‐Shane Yang,et al.  Excimer-Monomer Photoluminescence Mechanochromism and Vapochromism of Pentiptycene-Containing Cyclometalated Platinum(II) Complexes. , 2017, Inorganic chemistry.

[9]  Eugene E. Kwan,et al.  Macrocyclic bis-thioureas catalyze stereospecific glycosylation reactions , 2017, Science.

[10]  Yu‐Wu Zhong,et al.  H2PO4-- and Solvent-Induced Polymorphism of an Amide-Functionalized [Pt(N^C^N)Cl] Complex. , 2016, Inorganic chemistry.

[11]  Y. Mutoh,et al.  Synthesis and Shuttling Behavior of [2]Rotaxanes with a Pyrrole Moiety. , 2016, The Journal of organic chemistry.

[12]  S. Tunik,et al.  Solid-State and Solution Metallophilic Aggregation of a Cationic [Pt(NCN)L](+) Cyclometalated Complex. , 2016, Inorganic chemistry.

[13]  S. Goldup,et al.  Properties and emerging applications of mechanically interlocked ligands. , 2016, Chemical communications.

[14]  B. Heinrich,et al.  Green-blue light-emitting platinum(II) complexes of cyclometallated 4,6-difluoro-1,3-dipyridylbenzenes showing mesophase organisation , 2015 .

[15]  T. Takata,et al.  Synthesis and cavity size effect of Pd-containing macrocycle catalyst for efficient intramolecular hydroamination of allylurethane. , 2015, Organic letters.

[16]  Adrian B. Chaplin,et al.  Coordination induced atropisomerism in an NHC-based rhodium macrocycle , 2015 .

[17]  Adrian B. Chaplin,et al.  Synthesis and reactivity of NHC-based rhodium macrocycles. , 2015, Inorganic chemistry.

[18]  R. Kataky,et al.  Platinum(II) complexes of N^C^N-coordinating 1,3-bis(2-pyridyl)benzene ligands: thiolate coligands lead to strong red luminescence from charge-transfer states. , 2014, Inorganic chemistry.

[19]  Adrian B. Chaplin,et al.  Synthesis, structure and dynamics of NHC-based palladium macrocycles. , 2014, Dalton transactions.

[20]  Stephen J Benkovic,et al.  A clamp-like biohybrid catalyst for DNA oxidation. , 2013, Nature chemistry.

[21]  P. J. Lusby,et al.  Acid-base responsive switching between "3+1" and "2+2" platinum complexes. , 2013, Chemical communications.

[22]  J. Zyss,et al.  Tuning the dipolar second-order nonlinear optical properties of cyclometalated platinum(II) complexes with tridentate N^C^N binding ligands. , 2013, Chemistry.

[23]  L. J. Wright,et al.  Selective palladation of a large (32 ring atom) macrocyclic ligand at a bis(N-heterocyclic carbene) coordination pocket through transmetallation of the corresponding mercury(II) derivative. , 2012, Dalton transactions.

[24]  H. Takaya,et al.  Synthesis and Supramolecular Association of NCN-Pincer Pd-Complex-bound Norvaline Derivatives toward Fabrication of Controlled Metal Array , 2012 .

[25]  T. Takata,et al.  Successive catalytic reactions specific to Pd-based rotaxane complexes as a result of wheel translation along the axle. , 2010, Chemical communications.

[26]  M. Manassero,et al.  Reactivity of 1,3-bis(2-pyridyl)benzene, N--CH--N, with gold(III) chlorides: salts, adducts and cyclometalated pincer derivatives. Crystal and molecular structures of [HN--CH--N][AuCl4], [Au(N--C--N)Cl][PF6] and [Au(N--C--N)Cl(PPh3)2][PF6]. , 2009, Dalton transactions.

[27]  S. Saito,et al.  Synthesis, structure and catalytic activity of macrocyclic NHC PD pincer complexes , 2009 .

[28]  Y. Takashima,et al.  Polymerization of Lactones Initiated by Cyclodextrins: Effects of Cyclodextrins on the Initiation and Propagation Reactions , 2007 .

[29]  S. Nguyen,et al.  Supramolecular allosteric cofacial porphyrin complexes. , 2006, Journal of the American Chemical Society.

[30]  K. Ahn,et al.  Chiral Pt(II)/Pd(II) pincer complexes that show C–H⋯Cl hydrogen bonding: Synthesis and applications to catalytic asymmetric aldol and silylcyanation reactions , 2006 .

[31]  M. Manassero,et al.  The first pincer-aryl [M–(NCN)] complexes {M = Pd(II); Pt(II)} with chiral pyridine donors: Synthesis and catalytic activity in C–C bond formation , 2006 .

[32]  M. Manassero,et al.  Synthesis of the First C-2 Cyclopalladated Derivatives of 1,3-Bis(2-pyridyl)benzene. Crystal Structures of [Hg(N-C-N)Cl], [Pd(N-C-N)Cl], and [Pd2(N-C-N)2(μ-OAc)]2[Hg2Cl6]. Catalytic Activity in the Heck Reaction , 2005 .

[33]  T. Takata,et al.  Synthesis of novel interlocked systems utilizing a palladium complex with 2,6-pyridinedicarboxamide-based tridentate macrocyclic ligand , 2004 .

[34]  Alan E. Rowan,et al.  Epoxidation of polybutadiene by a topologically linked catalyst , 2003, Nature.

[35]  David Milstein,et al.  Cyclometalated phosphine-based pincer complexes: mechanistic insight in catalysis, coordination, and bond activation. , 2003, Chemical reviews.

[36]  M. Albrecht,et al.  Metallorganische Pinzetten‐Komplexe von Elementen der Platingruppe: Sensoren, Schalter und Katalysatoren , 2001 .

[37]  M. Albrecht,et al.  Platinum Group Organometallics Based on "Pincer" Complexes: Sensors, Switches, and Catalysts. , 2001, Angewandte Chemie.

[38]  Alan E. Rowan,et al.  A host-guest epoxidation catalyst with enhanced activity and stability , 2000 .

[39]  G. Yap,et al.  Calixarene Metalloreceptors. Synthesis and Molecular Recognition Properties of Upper-Rim Functionalized Calix[4]arenes Containing an Organopalladium Binding Site , 1997 .

[40]  M. Geoffroy,et al.  Synthesis and characterisation of a heterodinuclear ruthenium( II) - palladium( II) complex with two different cyclometallating sites , 1996 .

[41]  S. J. Loeb,et al.  SIMULTANEOUS FIRST- AND SECOND-SPHERE COORDINATION. ORGANOPALLADIUM METALLORECEPTORS FOR WATER, AMMONIA, AMINES, HYDRAZINE, AND THE HYDRAZINIUM ION , 1995 .

[42]  S. J. Loeb,et al.  SIMULTANEOUS FIRST- AND SECOND-SPHERE COORDINATION. ORGANOPALLADIUM CROWN ETHER COMPLEXES AS METALLORECEPTORS FOR O-AMINOPYRIDINE DERIVATIVES , 1994 .

[43]  J. Sauvage,et al.  Highly coupled mixed-valence dinuclear ruthenium and osmium complexes with a bis-cyclometalating terpyridine analog as bridging ligand , 1993 .

[44]  R. Kellogg,et al.  BINDING OF PTII VIA A SIGMA-PT-C BOND TO A NOVEL TYPE OF MACROCYCLIC MONOANIONIC CARBODIAZA LIGAND - X-RAY CRYSTAL-STRUCTURE OF TRANS-[2,6-(2,13-DIMETHYL-2,13-DIAZATETRADECANEDIYL)-PHENYL-N,N']PLATINUM(II) IODIDE , 1987 .

[45]  F. Kröhnke The Specific Synthesis of Pyridines and Oligopyridines1 , 1976 .

[46]  A. Chalk,et al.  Homogeneous Catalysis. II. The Mechanism of the Hydrosilation of Olefins Catalyzed by Group VIII Metal Complexes1 , 1965 .

[47]  F. Kröhnke Syntheses Using Pyridinium Salts (IV) , 1963 .