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Themed collection Organometallic and coordination chemistry of the s-block metals

21 items
Paper

Theoretical predictions of aromatic Be–O rings

We have carried out a theoretical investigation of benzene substituted with BeO to assess stability and aromatic properties (with 1–3 BeO units in a six-membered ring); C4H4BeO, C2H2Be2O2, and Be3O3.

Graphical abstract: Theoretical predictions of aromatic Be–O rings
Paper

Alkali metal complexes as efficient catalysts for hydroboration and cyanosilylation of carbonyl compounds

Catalytic hydroboration of aldehydes and ketones with pinacolborane (HBpin) and catalytic cyanosilylation of carbonyl compounds with trimethylsilyl cyanide using alkali metal (Li, Na, K) complexes as precatalysts under mild conditions are reported.

Graphical abstract: Alkali metal complexes as efficient catalysts for hydroboration and cyanosilylation of carbonyl compounds
Paper

Cyclooctatetraenyl calcium and strontium amido complexes

The first examples of Ca and Sr amido complexes built on a cyclooctatetraenyl platform are reported.

Graphical abstract: Cyclooctatetraenyl calcium and strontium amido complexes
Paper

Insertion of CS2 into the Mg–H bond: synthesis and structural characterization of the magnesium dithioformate complex, [TismPriBenz]Mg(κ2-S2CH)

Insertion of CS2 into the Mg–H bond of [TismPriBenz]MgH affords [TismPriBenz]Mg(κ2-S2CH), the first structurally characterized magnesium dithioformate compound.

Graphical abstract: Insertion of CS2 into the Mg–H bond: synthesis and structural characterization of the magnesium dithioformate complex, [TismPriBenz]Mg(κ2-S2CH)
Editorial

Organometallic and coordination chemistry of the s-block metals

Welcome to this issue of Dalton Transactions featuring the themed issue ‘Organometallic and Coordination Chemistry of the s-Block Metals’.

Graphical abstract: Organometallic and coordination chemistry of the s-block metals
Paper

Bulky cationic β-diketiminate magnesium complexes

Cationic β-diketiminate Mg complexes with the bulky tBuBDI ligand and the weakly coordinating anion B(C6F5)4 have been prepared by the reaction of (tBuBDI)MgnBu with [Ph3C]+[B(C6F5)4]; tBuBDI = CH[C(tBu)N-Dipp]2 and Dipp = 2,6-diisopropylphenyl.

Graphical abstract: Bulky cationic β-diketiminate magnesium complexes
Paper

5-Methyl-2-thienylcalcium iodide

Several preconditions are required to allow a high-yield synthesis of 2-thienylcalcium halide including protection of the 5-position by a methyl group and formation of a tetrahydropyran adduct.

Graphical abstract: 5-Methyl-2-thienylcalcium iodide
Paper

Amido Ca(II) complexes supported by Schiff base ligands for catalytic cross-dehydrogenative coupling of amines with silanes

Heteroleptic Ca(II) amides coordinated by multidentate phenolato ligands proved to be efficient catalysts for catalytic cross-dehydrogenative coupling of amines with silanes.

Graphical abstract: Amido Ca(ii) complexes supported by Schiff base ligands for catalytic cross-dehydrogenative coupling of amines with silanes
Communication

A facile synthesis for BeCl2, BeBr2 and BeI2

A facile synthesis for anhydrous berylliumhalides is presented and their vibrational spectra have been measured for the first time.

Graphical abstract: A facile synthesis for BeCl2, BeBr2 and BeI2
Paper

Synthesis and structural characterization of alkali metal arsinoamides

The alkali metal arsinoamide complexes [(Mes2AsNPh){Li(OEt2)2}], [(Mes2AsNPh){Na(OEt2)}]2, and [(Mes2AsNPh){K(THF)}]2 were synthesized.

Graphical abstract: Synthesis and structural characterization of alkali metal arsinoamides
Paper

1,4-Dihydropyridyl complexes of magnesium: synthesis by pyridine insertion into the magnesium–silicon bond of triphenylsilyls and catalytic pyridine hydrofunctionalization

Magnesium triphenylsilyl complexes [Mg(SiPh3)2(THF)2] and [(Me3TACD)Mg(SiPh3)] ((Me3TACD)H = 1,4,7-trimethyl-1,4,7,10-tetraazacyclododecane) serve as precursors for 1,4-dihydropyridyl complexes of magnesium which are active in the hydroboration of pyridine.

Graphical abstract: 1,4-Dihydropyridyl complexes of magnesium: synthesis by pyridine insertion into the magnesium–silicon bond of triphenylsilyls and catalytic pyridine hydrofunctionalization
Paper

Alkaline earth metal complexes stabilized by amidine and guanidine ligands: synthesis, structure and their catalytic activity towards polymerization of rac-lactide

Amidine ligands with various rigidity of backbone substituents were used to synthesize heteroleptic calcium complexes with different solvation and aggregation. These complexes unprecedentedly catalyze “immortal” ROP of lactide in the presence of excess PhOH.

Graphical abstract: Alkaline earth metal complexes stabilized by amidine and guanidine ligands: synthesis, structure and their catalytic activity towards polymerization of rac-lactide
Paper

Salt metathesis routes to homoleptic near-linear Mg(II) and Ca(II) bulky bis(silyl)amide complexes

A series of bulky bis(silyl)amide ligands have been utilised to stabilise rare examples of formally 2-coordinate linear or near-linear Mg and Ca complexes.

Graphical abstract: Salt metathesis routes to homoleptic near-linear Mg(ii) and Ca(ii) bulky bis(silyl)amide complexes
Paper

Well-defined styryl and biphenyl calcium complexes from dilithio compounds and calcium iodide: synthesis, structure and reactivity toward nitrous oxide

Efficient synthesis and structure elucidation of carbon–calcium σ-bonded compounds are of remarkable interest and importance in organometallic chemistry of the heavier s-block metals.

Graphical abstract: Well-defined styryl and biphenyl calcium complexes from dilithio compounds and calcium iodide: synthesis, structure and reactivity toward nitrous oxide
Open Access Paper

Alkali metal complexes based on bisheterocyclomethanide ligands

A series of new alkali metal complexes containing deprotonated bisheterocyclomethanide were synthesised and the potassium derivatives were exposed to hydrolysis.

Graphical abstract: Alkali metal complexes based on bisheterocyclomethanide ligands
Communication

Solvent-induced ion separation of a beryllium scorpionate complex

TpBeI undergoes a spontaneous ion separation upon treatment with THF, yielding [TpBe(thf)]I, which represents a rare example of a cationic beryllium complex.

Graphical abstract: Solvent-induced ion separation of a beryllium scorpionate complex
Perspective

s-Block metal complexes of PC(H)P-bridged chalcogen-centred methanides: comparisons with isoelectronic PNP-bridged monoanions

This Perspective compares the chemistries of s-block metal complexes of isoelectronic PC(H)P- and PNP-bridged, chalcogen-centred monoanions with a focus on the unique behavior of the C(H)-bridged systems.

Graphical abstract: s-Block metal complexes of PC(H)P-bridged chalcogen-centred methanides: comparisons with isoelectronic PNP-bridged monoanions
From the themed collection: 2018 Frontier and Perspective articles
Paper

Dimethylmagnesium revisited

Single-crystalline [MgMe2]n is obtained via crystallization from neat GaMe3, the formation of transient Mg(GaMe4)2 being indicated by the serendipitous isolation of octametallic [Mg(GaMe4)(OMe)]4.

Graphical abstract: Dimethylmagnesium revisited
Communication

Complexes between neutral oxyacid beryllium salts and dihydrogen: a possible way for hydrogen storage?

Very stable 1 : 1 and 1 : 2 complexes between oxyacid beryllium salts and H2 are found.

Graphical abstract: Complexes between neutral oxyacid beryllium salts and dihydrogen: a possible way for hydrogen storage?
Paper

The hetero-cubane structures of the heavy alkali metal tert-amyloxides [MOCMe2Et]4 (M = K, Rb, Cs)

Hetero-cubane structures were revealed for the tert-amyloxide compounds of potassium, rubidium, and caesium.

Graphical abstract: The hetero-cubane structures of the heavy alkali metal tert-amyloxides [MOCMe2Et]4 (M = K, Rb, Cs)
Paper

Straightforward synthesis of rubidium bis(trimethylsilyl)amide and complexes of the alkali metal bis(trimethylsilyl)amides with weakly coordinating 2,2,5,5-tetramethyltetrahydrofuran

2,2,5,5-Tetramethyl-THF (thf*) is a very bulky ether with a rather poor binding tendency due to weak basicity and steric hindrance. In the solid state, thf* complexes are observed whereas in solution these complexes dissociate.

Graphical abstract: Straightforward synthesis of rubidium bis(trimethylsilyl)amide and complexes of the alkali metal bis(trimethylsilyl)amides with weakly coordinating 2,2,5,5-tetramethyltetrahydrofuran
21 items

About this collection

This special issue of Dalton Transactions focusses on the field of alkali and alkaline earth metals. Guest edited by Sjoerd Harder (University Erlangen-Nürnberg) and Warren Piers (University of Calgary), this collection of reports in early main group metal chemistry is testimony to the increasing interest in this historically established field.

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