Themed collection Organometallic and coordination chemistry of the s-block metals
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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’.
Dalton Trans., 2018,47, 12491-12492
https://doi.org/10.1039/C8DT90148A
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.
Dalton Trans., 2018,47, 12493-12505
https://doi.org/10.1039/C7DT04791F
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.
Dalton Trans., 2018,47, 12506-12510
https://doi.org/10.1039/C8DT01756E
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.
Dalton Trans., 2018,47, 12516-12520
https://doi.org/10.1039/C8DT01679H
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.
Dalton Trans., 2018,47, 12511-12515
https://doi.org/10.1039/C8DT01640B
Lewis acidic alkaline earth metal complexes with a perfluorinated diphenylamide ligand
Alkaline earth metal chemistry with the anion [N(C6F5)2]− has been explored. Complexes are stabilized by metal⋯F interactions. Mg[N(C6F5)2]2 is a stronger Lewis acid than B(C6F5)3.
Dalton Trans., 2019,48, 6757-6766
https://doi.org/10.1039/C9DT01272A
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.
Dalton Trans., 2019,48, 5560-5568
https://doi.org/10.1039/C8DT03576H
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.
Dalton Trans., 2018,47, 12633-12641
https://doi.org/10.1039/C8DT02020E
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.
Dalton Trans., 2018,47, 12623-12632
https://doi.org/10.1039/C8DT01434E
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.
Dalton Trans., 2018,47, 12613-12622
https://doi.org/10.1039/C8DT02032A
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.
Dalton Trans., 2018,47, 12596-12605
https://doi.org/10.1039/C8DT01947A
Cyclooctatetraenyl calcium and strontium amido complexes
The first examples of Ca and Sr amido complexes built on a cyclooctatetraenyl platform are reported.
Dalton Trans., 2018,47, 12587-12595
https://doi.org/10.1039/C8DT02257G
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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.
Dalton Trans., 2018,47, 12606-12612
https://doi.org/10.1039/C8DT01678J
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.
Dalton Trans., 2018,47, 12582-12586
https://doi.org/10.1039/C8DT01545G
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.
Dalton Trans., 2018,47, 12570-12581
https://doi.org/10.1039/C8DT01130C
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.
Dalton Trans., 2018,47, 12562-12569
https://doi.org/10.1039/C8DT01539B
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.
Dalton Trans., 2018,47, 12546-12552
https://doi.org/10.1039/C8DT01542B
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.
Dalton Trans., 2018,47, 12553-12561
https://doi.org/10.1039/C8DT01466C
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.
Dalton Trans., 2018,47, 12540-12545
https://doi.org/10.1039/C8DT01046C
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.
Dalton Trans., 2018,47, 12534-12539
https://doi.org/10.1039/C8DT01398E
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.
Dalton Trans., 2018,47, 12526-12533
https://doi.org/10.1039/C8DT00802G
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.
Dalton Trans., 2018,47, 12521-12525
https://doi.org/10.1039/C7DT04401A
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.