Hiroyuki Matsuzaka

Rational Synthesis of Stable Channel‐Like Cavities with Methane Gas Adsorption Properties: [{Cu2(pzdc)2(L)}n] (pzdc=pyrazine‐2,3‐dicarboxylate; L=a Pillar Ligand)

Stable tunable channels are formed by pillared-layer-type coordination networks [{Cu2(pzdc)2(L)}n] (pzdc = pyrazine-2,3-dicarboxylate; L = pyrazine, 4,4′-bipyridine, N-(4-pyridyl)isonicotinamide). Not only their channel sizes, shapes, and chemical environments are systematically built up by tuning the pillar ligands, but also the porosity is maintained in the absence of the included guest molecules. These compounds can adsorb methane, and the amount of gas adsorption is controllable by the type of pillar ligands.

Rationale Synthese stabiler, kanalartiger Käfige mit Methan‐adsorbierenden Eigenschaften: [{Cu2(pzdc)2(L)}n] (pzdc=Pyrazin‐2,3‐dicarboxylat; L=Säulenligand)

Stabile Kanale mit einstellbaren Eigenschaften werden in [{Cu2(pzdc)2(L)}n]-Koordinationsnetzen des Saulen-Schicht-Typs gebildet (pzdc=Pyrazin-2,3-dicarboxylat; L=Pyrazin, 4,4′-Bipyridin oder N-(4-Pyridyl)isonicotinamid). Durch Wahl der Saulenliganden lassen sich Grose, Form und chemische Umgebung der Kanale systematisch einstellen; die Porositat bleibt auch ohne Gastmolekule erhalten. Die Verbindungen konnen Methan adsorbieren, und die adsorbierte Gasmenge ist durch die Art des Saulenliganden kontrollierbar.

Preparation and reactivity of dinuclear RuII complexes with bridging thiolate ligands [Cp★Ru(μ-SR)2RuCp★] (Cp★ η5-C5Me5; R iPr, tBu, 2,6-Me2C6H3).Oxidative addition of alkyl halides at the diruthenium center

Abstract Reactions of [Cp★RuCl] 4 (Cp★ ue5fb η 5 -C 5 Me 5 ) with NaSR (R ue5fb i Pr, t Bu, 2,6-Me 2 C 6 H 3 ) in THF afforded dinuclear Ru II complexes with two bridging thiolate ligands [Cp★Ru(μ-SR) 2 RuCp★] ( 3 ). An X-ray analysis of 3c (R = 2,6-Me 2 C 6 H 3 ) has disclosed the folded Ru 2 S 2 core structure with two equatorial C 6 H 3 Me 2 -2,6 groups in a solid state, while the results of variable-temperature 1 H NMR study are diagnostic of the fluxional nature of complexes 3 in solution resulting from the Ru 2 S 2 ring inversion. Complex 3a (R ue5fb i Pr) underwent oxidative addition of RX (R ue5fb PhCH 2 CH 2 or PhCH 2 , X ue5fb Br; R ue5fb Me or Et, X ue5fb I) and H 2 across the Ru 2 center to give [Cp★RuR(μ-S i Pr) 2 RuCp★X] ( 7 ) and [Cp★RuH(μ-S i Pr) 2 RuCp★H], respectively. The structure of 7a (R ue5fb PhCH 2 CH 2 , X ue5fb Br) has been determined by X-ray crystallography. Crystal data for 3c : space group P 4 2 / mnm , a = 15.307(4) A, c = 16.070(4) A, V = 3765(2) A 3 , Z = 4; 7a : space group P 2 1 / c , a = 10.348(2) A, b = 15.113(2) A, c = 22.340(5) A, β = 93.10(2)°, V = 3488(1) A 3 , Z = 4.

A New Anion‐Trapping Radical Host, [(Cu‐dppe)3{hat‐(CN)6}]2+

Anions PF6- and CF3 SO3- are trapped by the new radical host [(Cu-dppe)3 {hat-(CN)6 }]2+ , which was synthesized in a one-pot reaction from a copper(I) source, hat-(CN)6 , and dppe in acetone. The trapped salts have been characterized both in solution and in the solid state (see picture: A- : PF6- , CF3 SO3- ). hat-(CN)6 =hexaazatriphenylene hexacarbonitrile; dppe=1,2-bis(diphenylphosphanyl)ethane.

Towards novel organic synthesis on multimetallic centres: Syntheses and reactivities of dinuclear ruthenium thiolate complexes

From the reactions of [Cp★RuCl(μ2-Cl)2RuCp★Cl] (Cp★ = η5-C5Me5) with thiolate compounds, four types of thiolate-bridged diruthenium complexes have been obtained depending upon the thiolate source. These diruthenium complexes serve not only as a potential precursor for the synthesis of dinuclear disulfide-thiolate complexes and mixed-metal sulfide-thiolate clusters but also provide unique bimetallic reaction sites for the activation and transformations of various substrates such as alkynes, organic halides and H2.

Haldane gap systems

Abstract Haldane gap compounds with S =1 formulated as [Ni(AA) 2 X]Y ((AA) 2 =(diamines) 2 , linear-tetramines, N 4 -macrocycles; X=NO 2 and N 3 ; Y=ClO 4 , BF 4 and PF 6 ) and (CH 3 ) 4 N[Ni(NO 2 ) 3 ], and with S =2 formulated as [Mn(AA) 2 Cl 3 ] (AA=bipy and phen) are described. They have one-dimensional structures with bridging ligands. The Haldane conjecture was proven by magnetic susceptibility and high-field magnetization measurements. The magnitudes of the Haldane gap with S =1 can be controlled by combination of the bridging ligands, in-plane ligands, and counteranions as follows: X, N 3 >NO 2 ; AA, en≧tn>linear-tetramines>dmpn>Me 6 [14]aneN 4 ≧[15]aneN 4 ; Y, ClO 4 >PF 6 . In spite of a similar structure to Haldane gap compounds, the [Ni([15]aneN 4 )N 3 ]PF 6 and [Ni(en) 2 (NO 2 )]BF 4 species show spin-glass behavior, which is very novel in one-dimensional spin systems. The [Mn(bipy)Cl 3 ] is regarded as the first example of the Haldane gap system with S =2.

Synthesis of benzofurans and benzothiophenes by palladium catalyzed cyclocarbonylation of 3-furylallyl and 3-thienylallyl acetates☆

Abstract Acetoxybenzofurans and acetoxybenzothiophenes were obtained in good yields by palladium catalyzed cyclocarbonylation of 3-furylallyl and 3-thienylallyl acetates, respectively.

Syntheses and electronic structures of macrocyclic metal complexes with fullerene

Abstract New cocrystallines are reported that contain C 60 with anti-formed macrocyclic metal complexes of octaethylporphyrin (OEP). From the results of the electronic structure obtained using a DV-Xα molecular orbital calculation, the configuration of the OEP in a cocrystalline of C 60 with Ag(II)(OEP) or Ni(II)(OEP) is predicted to be the anti-formed structure. It is shown that the anti-formed configuration of the OEPs can be confirmed in Ag(II)(OEP)·C 60 ·2C 6 H 6 and 2Ni(II)(OEP)·C 60 ·2C 6 H 5 Cl according to a structural prediction we have made by means of electronic structure calculations using the DV-Xα method. It is also revealed that the C 60 is located at the closest approach to the centered atom involving the 5:6 carbon ring junction in these cocrystallines. Using the DV-Xα method, it is predicted that new types of π–d material can be produced. The material should have high conductivity and a significant magnetic moment via the π–d interaction in the charge transfer salt of [Cr(III)(Por)] + [C 60 ] − .

Homogeneous multimetallic catalysts: Part 9.1 Hydroformylation of norbornene by cobalt-ruthenium bimetallic catalyst

Afin dobtenir des informations sur le mecanisme de leffet de synergie du catalyseur bimetallique constitue de cobalt et de ruthenium, lhydroformylation du norbornene par Co 2 (CO) 8 -Ru 3 (CO) 12 est etudiee

Chemistry of cobalt-ruthenium mixed metal complexes: Carbonylation and metalloselective substitution reactions

Abstract The reaction of RuCl 3 with 4 molar equivalents of Na[Co(CO) 4 ] gives a mixed cluster Na[RuCo 3 (CO) 12 ] in high yield. The cluster readily undergoes a cation exchange by bulky cations such as [(Ph 3 P) 2 N] + , while protonolysis by phosphoric acid produces HRuCo 3 (CO) 12 . The X-ray structure of [(Ph 3 P) 2 N][RuCo 3 (CO) 12 ] shows that the four metals are located at the corners of a tetrahedron. These mixed clusters are very effective for the homologation of methanol compared with Co 2 (CO) 8 . On the other hand, the Co 2 (CO) 8 ue5f8Ru 3 (CO) 12 bimetallic catalyst shows remarkably high catalytic activity for hydroformylation of olefins such as cyclohexene compared with Co 2 (CO) 8 alone. The synergistic effects for cobalt and ruthenium on these carbonylation reactions dre discussed. Metalloselective substitution reactions were observed when HRuCo 3 (CO) 12 was treated with amines or phosphines. The substitution of amines for the carbonyl ligand takes place preferentially at the ruthenium atom whereas the substitution of phosphines occurs exclusively at the cobalt atoms.