Unprecedented layered coordination polymers of dithiolene group 10 metals: Magnetic and electrical properties

One-pot reactions between Ni(ii), Pd(ii) or Pt(ii) salts and 3,6-dichloro-1,2-benzenedithiol (HSC6H2Cl2SH) in KOH medium under argon lead to a series of bis-dithiolene coordination polymers. X-ray analysis shows the presence of a common square planar complex [M(SC6H2Cl2S)2]2- linked to potassium cations forming either a two-dimensional coordination polymer network for {[K2(μ-H2O)2(μ-thf)(thf)2][M(SC6H2Cl2S)2]}n [M = Ni (1) and Pd (2)] or a one-dimensional coordination polymer for {[K2(μ-H2O)2(thf)6][Pt(SC6H2Cl2S)2]}n (3). In 3 the coordination environment of the potassium ions may slightly change leading to the two-dimensional coordination polymer {[K2(μ-H2O)(μ-thf)2][Pt(SC6H2Cl2S)2]}n (4) that crystallizes together with 3. The physical characterization of compounds 1-3 show similar trends, they are diamagnetic and behave as semiconductorsWe thank financial support from MICINN (MAT2013-46753-C2-1-P, CTQ2014-52758-P and MAT2014-56143-R) and Generalitat Valenciana (PrometeoII/2014/076

Procedimiento de aplicación de sepiolitas básicas como catalizadores en reacciones de condensación de Knoevenagel

Referencia OEPM: P8904192.-- Fecha de solicitud: 12/12/1989.-- Titular: Consejo Superior de Investigaciones Científicas (CSIC).El procedimiento de invención se refiere a la aplicación de sepiolitas básicas como catalizadores en reacción de condensación de Knoevenagel. Las sepiolitas empleadas se obtienen mediante modificación de la sepiolita natural con iones alcalinos o alcalinotérreos. Estos catalizadores poseen una elevada área superficial y un elevado volumen de poro.Peer reviewe

Structural diversity of compounds based on iron-dithiolene with sodium or potassium complexes

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Crystal Growth and Design, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see: https://pubs.acs.org/doi/abs/10.1021/acs.cgd.6b00921A series of iron dithiolene compounds with sodium or potassium complexes have been prepared by direct reactions. Their structures consist of coordination polymers of different dimensionalities or molecular compounds depending on the nature of the iron precursor, the presence or not of a donor substituent in the aromatic ring of the dithiolene ligand, and the amount of water molecules present during the crystallization. Since all these compounds are based on the combination of cationic alkaline and anionic iron-dithiolene entities that connect each other by coordination bonds, in order to favor local electroneutrality the structures obtained show that charged entities with a similar charge/size ratio pack more effectively. The flexibility of the potassium coordination environment seems to facilitate the structural diversity found for this family of compounds.Financial support from Spain’s MICINN (MAT2013-46753-C2-1-P and MAT2013-46502-C2-1-P) and Factoría de Cristalización (CONSOLIDER-INGENIO 2010) is gratefully acknowledged

Cadmium and mercury complexes containing trinuclear titanium imido-nitrido metalloligands

Several heterometallic nitrido complexes have been prepared from the reaction of the trinuclear imido-nitrido titanium complex [{Ti(5-C5Me5)(mu-NH)}3(mu 3-N)] (1) with cadmium and mercury derivatives. Treatment of 1 with cadmium dichloride or cadmium diiodide in toluene afforded the adducts [X2Cd{(mu 3-NH)3Ti3(5-C5Me5)3(mu 3-N)}] [X = Cl (2), I (3)]. Complex 2 reacted with lithium reagents [LiR] in toluene to give the cube-type derivatives [RCd{(mu 3-N)(mu 3-NH)2Ti3(5-C5Me5)3(mu 3-N)}] [R = CH2SiMe3 (4), C=CSiMe3 (5), C5H4(SiMe3) (6), N(SiMe3)2 (7)]. The amido complex 7 reacted with 1 equiv. of 1 to give the corner-shared double-cube complex [Cd{(mu 3-N)(mu 3-NH)2Ti3(5-C5Me5)3(rho 3-N)}2] (8) by means of bis(trimethylsilyl)amine elimination. Treatment of 1 with mercury(II) iodide in toluene gave the adduct [I2Hg{(mu 3-NH)3Ti3(5-C5Me5)3(mu 3-N)}] (9), which reacted with [K{N(SiMe3)2}] to afford [Hg{(mu 3-N)2Ti3(5-C5Me5)3(mu-NH)(mu 3-N)}]2 (10) through the amido mercury intermediate [{(Me3Si)2N}Hg{(mu 3-N)Ti3(5-C5Me5)3(mu-NH)2(mu 3-N)}] (11). Compound 11 and the analogous alkyl derivative [(Me3SiCH2)Hg{(mu 3-N)Ti3(5-C5Me5)3(mu-NH)2(mu 3-N)}] (12) were characterised by NMR spectroscopy upon the treatment of 1 with [Hg{N(SiMe3)2}R] [R = N(SiMe3)2, CH2SiMe3]. Complex [Hg{(mu 3-N)Ti3(5-C5Me5)3(mu-NH)2(mu 3-N)}2] (13), with one bridging mercury atom between two titanium trinuclear systems, was obtained upon treatment of HgI2 with the potassium derivative [K(mu 4-N)(mu 3-NH)2{Ti3(5-C5Me5)3(mu 3-N)}]2. Complexes 3, 5 and 8 were characterised by single-crystal X-ray diffraction analysis.Ministerio de Educación y Ciencia de Españ

Molecular Nitrides with Titanium and Group 13-15 Elements

MINISTERIO DE EDUCACIÓN Y CIENCIA, COMUNIDAD DE MADRID, UNIVERSIDAD DE ALCAL

Synthesis and structural characterization of transition metal dithiolene derivatives containing divalent metals as counter-cations

Direct reactions between HSC 6 H 2 Cl 2 SH, FeCl 3 ·6H 2 O and divalent metal bases lead to the formation of the cation-anion metal-dithiolene complexes [Ca(H 2 O) 3 (OCMe 2 ) 4 ][Fe 2 (SC 6 H 2 Cl 2 S) 4 ]·3OCMe 2 and [Zn(DMF) 6 ][Fe 2 (SC 6 H 2 Cl 2 S) 4 ], as well as the molecular compound [Ba(OCMe 2 ) 6 ][Fe 2 (SC 6 H 2 Cl 2 S) 4 ], instead of metal-dithiolene coordination polymers as compared with results previously obtained when alkali metals, under similar conditions, were used. An alternative synthetic route based on the reactions between K 2 [Fe 2 (SC 6 H 2 Cl 2 S) 4 ] and ZnCl 2 ·6H 2 O or NiCl 2 ·6H 2 O was also evaluated, giving rise to the ion-pair compounds [Fe(H 2 O) 2 (THF) 4 ][Ni(SC 6 H 2 Cl 2 S) 2 ] 2 ·4THF and [Fe(H 2 O) 4 (THF) 2 ][Fe 2 (SC 6 H 2 Cl 2 S) 4 ]·4THF and the coordination polymer {[K 2 (THF) 8 ][Zn 6 (μ-Cl) 2 (SC 6 H 2 Cl 2 S) 4 (μ-κO:κO-SC 6 H 2 Cl(ClO 2 )S) 2 ]} n . It is interesting to remark that in the last compound the oxidation of one Cl substituent of a dithiolene ligand resulted in the formation of a Cl(O) 2 groupThis work was supported in part by MICINN (grant MAT2016-77608-C3-1-P

Cube-Type Nitrido Complexes Containing Titanium and Alkali/Alkaline-Earth Metals

(M = Ca, Sr) have been determined. The properties and solid-state structures of the azaheterometallocubane complexes bearing alkali and alkaline-earth metals are discussed.Ministerio de Ciencia y Tecnología de España, Comunidad de Madrid, Universidad de Alcal

Amido-bridged double cube nitrido complexes containing titanium and magnesium/calcium

Treatment of the single cube nitrido complexes [(thf)(x){(Me3Si)(2)N} M{(mu(3)-N)(mu(3)-NH)(2)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (M = Mg, x = 0; Ca, x = 1) with one equivalent of anilines NH2Ar in toluene affords the arylamido complexes [(ArHN) M{(mu(3)-N)(mu(3)- NH)(2)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}](n) [M = Mg ( 3), n = 1, Ar = 4-MeC6H4; Ca (4), n = 2, Ar = 2,4,6-Me3C6H2]. The magnesium complex 3 has a single-cube structure whereas the X-ray crystal structure of the analogous calcium derivative 4 shows two cube-type azaheterometallocubane moieties "Ca{(mu(3)-N)(mu(3)- NH)(2)Ti-3(eta(C5Me5)-C-5) (3)(mu(3)-N)}" held together by two mu-2,4,6-trimethylanilido ligands. Complexes 3 and 4 react with chloroform-d(1) at room temperature to give the metal halide adducts [Cl2M{(mu(3)-NH)(3)Ti-3(eta(5)-C5Me5)(3)(mu(3)- N)}] (M = Mg, Ca). A solution of 3 in n-hexane gave complex [{Mg-2(mu(3)-N)(mu(3)-NH)(5)[ Ti-3(eta(5)- C5Me5)(3)(mu(3)- N)](2)}(mu-NHAr)(3)] which shows three mu-4-methylanilido ligands bridging two [MgTi3N4] cube type cores according to an X-ray crystal structure determination.Ministerio de Ciencia y Tecnología, Comunidad de Madri

From well-defined clusters to functional materials: molecular Engineering of amorphous molybdenum sulfides for hydrogen evolution Electrocatalysis

Developing precious-metal-free electrocatalysts for the hydrogen evolution reaction (HER) is crucial to establishing H2 produced from renewable energy sources as an alternative energy carrier to fossil fuels. Amorphous molybdenum sulfide-based materials are promising candidates that provide highly active HER electrocatalysts by introducing active sites at both the edge positions and the typically inactive basal planes. Herein, we report an innovative bottom-up synthesis of amorphous molybdenum sulfides using molecular complexes with Mo3S4 and Mo3S7 cluster cores as building entities. The ability to control the precursor of choice has made it viable to enhance the HER activity of these materials. Furthermore, the tunability of the atomic composition of the molecular cluster precursors allows the modification of the derived materials with atomic-scale precision, enabling us to track the synthesis mechanism and, in combination with Density Functional Theory (DFT) calculations, to decipher the nature of the HER active sites

Copper(I) and Silver(I) Complexes Supported by the Tridentate [{Ti(η5-C5Me5)(μ-NH)}3(μ3-N)] Metalloligand

(2) (M = Cu (18), Ag (19)). The X-ray crystal structures of 4, 5, 10, 14, 15, and 18 have been determined.Ministerio de Educación y Ciencia de Españ