Main Group Metal Chemistry Research Articles

Calcium-Ligand Cooperation Promoted Activation of N2O, Amine, and H2 as well as Catalytic Hydrogenation of Imines, Quinoline, and Alkenes.

Bond activation and catalysis using s-block metals are of great significance. Herein, a series of calcium pincer complexes with deprotonated side arms have been prepared using pyridine-based PNP and PNN ligands. The complexes were characterized by NMR and X-ray crystal diffraction. Utilizing the obtained calcium complexes, unprecedented N2O activation by metal-ligand cooperation (MLC) involving dearomatization-aromatization of the pyridine ligand was achieved, generating aromatized calcium diazotate complexes as products. Additionally, the dearomatized calcium complexes were able to activate the N-H bond as well as reversibly activate H2, offering an opportunity for the catalytic hydrogenation of various unsaturated molecules. DFT calculations were applied to analyze the electronic structures of the synthesized complexes and explore possible reaction mechanisms. This study is an important complement to the area of MLC and main-group metal chemistry.

Synthesis and Modular Reactivity of Low Valent Al/Zn Heterobimetallics Supported by Common Monodentate Amides.

Recent advances on low valent main group metal chemistry have shown the excellent potential of heterobimetallic complexes derived from Al(I) to promote cooperative small molecule activation processes. A signature feature of these complexes is the use of bulky chelating ligands which act as spectators providing kinetic stabilization to their highly reactive Al-M bonds. Here we report the synthesis of novel Al/Zn bimetallics prepared by the selective formal insertion of AlCp* into the Zn-N bond of the utility zinc amides ZnR2 (R=HMDS, hexamethyldisilazide; or TMP, 2,2,6,6-tetramethylpiperidide). By systematically assessing the reactivity of the new [(R)(Cp*)AlZn(R)] bimetallics towards carbodiimides, structural and mechanistic insights have been gained on their ability to undergo insertion in their Zn-Al bond. Disclosing a ligand effect, when R=TMP, an isomerization process can be induced giving [(TMP)2AlZn(Cp*)] which displays a special reactivity towards carbodiimides and carbon dioxide involving both its Al-N bonds, leaving its Al-Zn bond untouched.

Alkali Metal Metal(ates) Containing Divalent Earth Abundant Transition Metals

Recent advances in cooperative chemistry have shown the enormous potential of main group heterobimetallic complexes for the functionalisation of aromatic molecules. Going beyond main group metal chemistry, here we provide an overview on the synthesis, structure and reactivity of bimetallic complexes which combine an alkali-metal (AM= Li, Na) with a divalent earth-abundant transition metal (M= Mn, Fe, Co, Ni), containing the utility silyl amide HMDS (HMDS = N(SiMe3)2). Advancing the understanding on how cooperative effects operate in these bimetallic (ate) systems, selected examples of their applications in deprotonative metalation are also discussed with special emphasis on the constitution of the metalated intermediates.

Alkali-Metal Mediation: Diversity of Applications in Main-Group Organometallic Chemistry.

Organolithium compounds have been at the forefront of synthetic chemistry for over a century, as they mediate the synthesis of myriads of compounds that are utilised worldwide in academic and industrial settings. For that reason, lithium has always been the most important alkali metal in organometallic chemistry. Today, that importance is being seriously challenged by sodium and potassium, as the alkali‐metal mediation of organic reactions in general has started branching off in several new directions. Recent examples covering main‐group homogeneous catalysis, stoichiometric organic synthesis, low‐valent main‐group metal chemistry, polymerization, and green chemistry are showcased in this Review. Since alkali‐metal compounds are often not the end products of these applications, their roles are rarely given top billing. Thus, this Review has been written to alert the community to this rising unifying phenomenon of “alkali‐metal mediation”.

ChemInform Abstract: Molecular Early Main Group Metal Hydrides: Synthetic Challenge, Structures and Applications

AbstractReview: 99 refs.

Molecular early main group metal hydrides: synthetic challenge, structures and applications

Within the general area of early main group metal chemistry, the controlled synthesis of well-defined metal hydride complexes is a rapidly developing research field. As group 1 and 2 metal complexes are generally highly dynamic and lattice energies for their [MH](∞) and [MH(2)](∞) salts are high, the synthesis of well-defined soluble hydride complexes is an obvious challenge. Access to molecular early main group metal hydrides, however, is rewarding: these hydrocarbon-soluble metal hydrides are highly reactive, have found use in early main group metal catalysis and are potentially also valuable molecular model systems for polar metal hydrides as a hydrogen storage material. The article focusses specifically on alkali and alkaline-earth metal hydride complexes and discusses the synthetic challenge, molecular structures, reactivity and applications.

A new start for Main Group Metal Chemistry

A new start for Main Group Metal Chemistry

Me4NHWO4SnPh3X (X=Cl, Br), R4NWO4SnPh3 (R=Me, Et) and (Snbu3)2WO4: Synthesis and Spectroscopic Studies

Article Me4NHWO4SnPh3X (X=Cl, Br), R4NWO4SnPh3 (R=Me, Et) and (Snbu3)2WO4: Synthesis and Spectroscopic Studies was published on April 1, 2010 in the journal Main Group Metal Chemistry (volume 33, issue 1-2).

Synthesis and Spectroscopic Structural Elucidation of New Class of Mono-and Heterobinuclear Derivatives of Arsenic and Aluminium Derived from Bifunctional Tridentate Schiff Base Ligands

Article Synthesis and Spectroscopic Structural Elucidation of New Class of Mono-and Heterobinuclear Derivatives of Arsenic and Aluminium Derived from Bifunctional Tridentate Schiff Base Ligands was published on April 1, 2010 in the journal Main Group Metal Chemistry (volume 33, issue 1-2).

Synthesis, Crystal Structure and Theoretical Study of Al(III) Complex with (2-(2-hydroxyphenyl) benzimidazolate Cocrystallized by DMF Solvate

Article Synthesis, Crystal Structure and Theoretical Study of Al(III) Complex with (2-(2-hydroxyphenyl) benzimidazolate Cocrystallized by DMF Solvate was published on April 1, 2010 in the journal Main Group Metal Chemistry (volume 33, issue 1-2).

Extraction and Carrier Facilitated Membrane Transport Studies of Some Biologically Important Metal Ions (Na+, K+ and Ca2+) using Redox Switched Ionophore

Article Extraction and Carrier Facilitated Membrane Transport Studies of Some Biologically Important Metal Ions (Na+, K+ and Ca2+) using Redox Switched Ionophore was published on December 1, 2010 in the journal Main Group Metal Chemistry (volume 33, issue 6).

Snr2(O2phph)2 (R=Me, Bu), Snbu3o2phph, Me4NO2PHPh.2snph3cl and Cy2NH2SnPh2(O2phph)3 Synthesis and Spectroscopic Studies

Article Snr2(O2phph)2 (R=Me, Bu), Snbu3o2phph, Me4NO2PHPh.2snph3cl and Cy2NH2SnPh2(O2phph)3 Synthesis and Spectroscopic Studies was published on April 1, 2010 in the journal Main Group Metal Chemistry (volume 33, issue 1-2).

Synthesis, Infrared and Mössbauer Studies of New Mono- Di- and Trinuclear Oxalato Triphenyltin (Iv) Derivatives

Article Synthesis, Infrared and Mössbauer Studies of New Mono- Di- and Trinuclear Oxalato Triphenyltin (Iv) Derivatives was published on October 1, 2010 in the journal Main Group Metal Chemistry (volume 33, issue 4-5).

Synthesis, Spectral and Antimicrobial Studies of Mixed-ligand Complexes of Antimony (III) with |3(2'-hydroxyphenyl)-5-(4-substituted phenyl) pyrazolines| and 2-(N-salicylidine)-5- Chlorobenzophenone

Article Synthesis, Spectral and Antimicrobial Studies of Mixed-ligand Complexes of Antimony (III) with |3(2'-hydroxyphenyl)-5-(4-substituted phenyl) pyrazolines| and 2-(N-salicylidine)-5- Chlorobenzophenone was published on April 1, 2010 in the journal Main Group Metal Chemistry (volume 33, issue 1-2).

On the Existence of « Tetrahedral » SnMe2(PhCO2)2 and |SnMe2(PhCO2)3| in New Benzoato Adducts: Synthesis and Spectroscopic Studies

Article On the Existence of « Tetrahedral » SnMe2(PhCO2)2 and |SnMe2(PhCO2)3| in New Benzoato Adducts: Synthesis and Spectroscopic Studies was published on December 1, 2009 in the journal Main Group Metal Chemistry (volume 32, issue 6).

Et4NC2O4SnPh3.2SnPh3Cl and Cy2NH2C2O4SnPh3.2SnPh3Cl: Synthesis and Spectroscopic Characterization

Article Et4NC2O4SnPh3.2SnPh3Cl and Cy2NH2C2O4SnPh3.2SnPh3Cl: Synthesis and Spectroscopic Characterization was published on August 1, 2009 in the journal Main Group Metal Chemistry (volume 32, issue 4).

Synthesis and Spectroscopic Structural Elucidation of Some Novel Heterobimetallic Complexes of Monoorganotin (IV)

Article Synthesis and Spectroscopic Structural Elucidation of Some Novel Heterobimetallic Complexes of Monoorganotin (IV) was published on October 1, 2009 in the journal Main Group Metal Chemistry (volume 32, issue 5).

Synthesis and Characterization of Penta- and Hexa- Coordinated Silicon Compounds with Schiff Bases Containing -NCS Functionality

Article Synthesis and Characterization of Penta- and Hexa- Coordinated Silicon Compounds with Schiff Bases Containing -NCS Functionality was published on April 1, 2009 in the journal Main Group Metal Chemistry (volume 32, issue 2).

The Bio Side of 9,10-Diaminophenanthrene Derivatives of Bivalent Tin : Synthetic Route, Spectroscopic Characterization and Applied Aspects with Toxicological Screening

Article The Bio Side of 9,10-Diaminophenanthrene Derivatives of Bivalent Tin : Synthetic Route, Spectroscopic Characterization and Applied Aspects with Toxicological Screening was published on February 1, 2009 in the journal Main Group Metal Chemistry (volume 32, issue 1).

Interactions between (Me4N)2C2O4.SnPh2C2O4.H2O and some Lewis acids: Synthesis, IR and Mossbauer studies of new trinuclear dioxalato complexes

Article Interactions between (Me4N)2C2O4.SnPh2C2O4.H2O and some Lewis acids: Synthesis, IR and Mossbauer studies of new trinuclear dioxalato complexes was published on October 1, 2009 in the journal Main Group Metal Chemistry (volume 32, issue 5).