Themed collection Inorganic chemistry of the p-block elements
Inorganic chemistry of the p-block elements
This special web collection of Dalton Transactions focuses on the inorganic chemistry of the p-block elements, as a tribute to the 150th anniversary of the development of the periodic table.
Dalton Trans., 2019,48, 6666-6668
https://doi.org/10.1039/C9DT90098E
Neutral binary chalcogen–nitrogen and ternary S,N,P molecules: new structures, bonding insights and potential applications
This perspective evaluates the results of recent investigations of binary chalcogen–nitrogen molecules, especially nitrogen-rich systems, with a focus of new structures, bonding insights and applications.
Dalton Trans., 2020,49, 6532-6547
https://doi.org/10.1039/D0DT00807A
Transition metal catalysed direct selanylation of arenes and heteroarenes
Recent outstanding advances in the C–Se bond formation through transition metalcatalysed direct selanylation, providing new insights into their mechanistic aspects, were provided in this perspective.
Dalton Trans., 2019,48, 9851-9905
https://doi.org/10.1039/C9DT00473D
Telluraporphyrinoids: an interesting class of core-modified porphyrinoids
This perspective presents a concise overview of the developments in telluraporphyrinoid chemistry since its inception.
Dalton Trans., 2019,48, 4444-4459
https://doi.org/10.1039/C9DT00079H
Heavier pnictogens – treasures for optical electronic and reactivity tuning
We highlight recent advances in organopnictogen chemistry contrasting the properties of lighter and heavier pnictogens.
Dalton Trans., 2019,48, 4460-4466
https://doi.org/10.1039/C9DT00574A
On the activation of hypercoordinate iodine(III) compounds for reactions of current interest
Mechanistic insights into different modes of activation of hypercoordinate iodine(III) compounds.
Dalton Trans., 2019,48, 4086-4093
https://doi.org/10.1039/C9DT00472F
The influence of ring strain on the formation of Si–H–Si stabilised oligosilanylsilyl cations
Ring strain wins over entropy in the formation of inter- vs. intramolecularly 3c2e Si–H–Si bridged oligosilanylsilyl cations.
Dalton Trans., 2021,50, 16509-16513
https://doi.org/10.1039/D1DT03375A
The formation of a 1,4-disilabenzene and its isomerization into a disilabenzvalene derivative
A stable 1,4-disilabenzene was generated from the reaction of a stable disilyne with 3-hexyne.
Dalton Trans., 2019,48, 9053-9056
https://doi.org/10.1039/C9DT01322A
Lighting with organophosphorus materials: solution-processed blue/cyan light-emitting devices based on phosphaphenalenes
The suitability of phosphaphenalene derivatives for light-emitting diodes and electrofluorochromic devices is herein demonstrated.
Dalton Trans., 2019,48, 7503-7508
https://doi.org/10.1039/C9DT00380K
Successive carbene insertion into 9-phenyl-9-borafluorene
The reactions of 9-phenyl-9-borafluorene with trimethylsilyldiazomethane in a 1 : 1 and 1 : 2 stoichiometry furnished the corresponding BC5 and BC6 heterocycles via the formal insertion of one and two carbene units.
Dalton Trans., 2019,48, 6319-6322
https://doi.org/10.1039/C9DT01032G
Synthesis of a hydrogen-bridged tetraborane(6): a substituent effect of a diaminoboryl group toward the B–B multiple bond character
A hydrogen-bridging tetraborane(6) was synthesized from boryllithium, a boron nucleophile, in three steps.
Dalton Trans., 2019,48, 5496-5499
https://doi.org/10.1039/C9DT01117J
A turn-on phosphorescent sensor of Pb2+ in water by the formation of a coordination polymer
Persulfurated asterisks functionalized with six carboxylic groups form a strongly green phosphorescent coordination polymer upon addition of Pb2+ ions in aqueous solution. The self-assembly process is selective and reversible, enabling Pb2+ sensing with a detection limit of 6.0 × 10−7 M.
Dalton Trans., 2019,48, 3815-3818
https://doi.org/10.1039/C9DT00251K
Redox chemistry of an anionic dithiolene radical
The redox reactivity of a stable anionic dithiolene radical has been explored, giving the corresponding dithiolate and neutral dithiolene dimers.
Dalton Trans., 2019,48, 3543-3546
https://doi.org/10.1039/C8DT04989K
Germylone-bridged bimetallic Ir and Rh complexes
The reactions of germylone 1 with one equivalent of [M(COD)Cl]2 (M = Ir, Rh) afforded the germylone-bridged bimetallic complexes 2 and 3, which have been spectroscopically and structurally characterized.
Dalton Trans., 2019,48, 3555-3559
https://doi.org/10.1039/C9DT00145J
Highly soluble Cu(I)-acetonitrile salts as building blocks for novel phosphorus-rich organometallic-inorganic compounds
The synthesis of the highly soluble salts [Cu(CH3CN)3.5][FAl{OC(C6F10)(C6F5)}3] and [Cu(CH3CN)4][Al{OC(CF3)3}4] is presented. These compounds react with polyphosphorus ligand complexes to form pristine phosphorus-rich Cu(I) dimers.
Dalton Trans., 2018,47, 16031-16035
https://doi.org/10.1039/C8DT03723J
Coordination chemistry and structural rearrangements of the Me2PCH2AlMe2 ambiphilic ligand
Reactions between (Me2PCH2AlMe2)2 and late transition metal complexes led to five distinct outcomes, ranging from Me2PCH2AlMe2 coordination to in situ generation of a tris(phosphino)aluminate ligand.
Dalton Trans., 2022,51, 15040-15048
https://doi.org/10.1039/D2DT02519A
Molecular enneanuclear CuII phosphates containing planar hexanuclear and trinuclear sub-units: syntheses, structures, and magnetism
Highly symmetric enneanuclear copper(II) phosphates comprising of a hexanuclear and a trinuclear motif are described.
Dalton Trans., 2020,49, 2527-2536
https://doi.org/10.1039/C9DT04584H
Neutral and cationic phosphine and arsine complexes of tin(IV) halides: synthesis, properties, structures and anion influence
A series of tin(IV) halide complexes with mono- and bidentate pnictine ligands and the influence of various halide abstractors on these is discussed, together with DFT calculations to probe the HOMO/LUMO energies in the resulting species.
Dalton Trans., 2019,48, 17097-17105
https://doi.org/10.1039/C9DT03683K
Structure and bonding in reduced boron and aluminium complexes with formazanate ligands
A comparison of structure and bonding in reduced formazanate B/Al complexes and their ligand-benzylated products is described. The kinetics of homolytic N–C(benzyl) bond cleavage in the latter compounds is studied.
Dalton Trans., 2019,48, 13981-13988
https://doi.org/10.1039/C9DT02831E
Electrostatic polarization of nonpolar substrates: a study of interactions between simple cations and Mo-bound N2
Dinitrogen, one of the most nonpolar ligands in coordination chemistry, is known to be affected by electrostatic interactions in both heterogeneous and homogeneous reactions, but the significance of these effects is still poorly understood.
Dalton Trans., 2019,48, 11004-11017
https://doi.org/10.1039/C9DT01606F
Modular triazine-based carborane-containing carboxylic acids – synthesis and characterisation of potential boron neutron capture therapy agents made of readily accessible building blocks
Boron-rich carboxylic acid derivatives were synthesised as coupling partners for tumour-selective biomolecules with applications as selective BNCT agents.
Dalton Trans., 2019,48, 10834-10844
https://doi.org/10.1039/C9DT02130B
Mesityl(amidinato)tetrylenes as ligands in iridium(I) and iridium(III) complexes: silicon versus germanium and simple κ1-coordination versus cyclometallation
The reactivity of the germylene Ge(tBu2bzam)Mes with [Ir2(μ-Cl)2(η4-cod)2] and [Ir2Cl2(μ-Cl)2(η5-Cp*)2] differs considerably from that previously communicated for the isostructural silylene Si(tBu2bzam)Mes.
Dalton Trans., 2019,48, 10996-11003
https://doi.org/10.1039/C9DT01853K
Oxidation behavior of intramolecularly coordinated unsymmetrical diorganotellurides: isolation of novel tetraorganoditelluronic acids, [RR′Te(μ-O)(OH)2]2
The synthesis of a series of tetraorganoditelluronic acids, [RR′Te(μ-O)(OH)2]2 has been reported.
Dalton Trans., 2019,48, 10979-10985
https://doi.org/10.1039/C9DT01926J
Versatile coordinating abilities of acyclic N4 and N2P2 ligand frameworks in conjunction with Sn[N(SiMe3)2]2
The conjoint effort of the –CH2–CH2– linker backbone and coordinating sites in the tetradentate ligand stabilizes a variety of stannylenes.
Dalton Trans., 2019,48, 10953-10961
https://doi.org/10.1039/C9DT00617F
Solvent-tailored Pd3P0.95 nano catalyst for amide–nitrile inter-conversion, the hydration of nitriles and transfer hydrogenation of the CO bond
First synthesis of Pd3P0.95 QDs via solvent-controlled SSP and their three applications as catalysts (1–2 mol% of Pd) for substrates >10 are reported.
Dalton Trans., 2019,48, 10962-10970
https://doi.org/10.1039/C8DT04667K
Reactions of a tetrasilabicyclo[1.1.0]but-1(3)-ene with carbon tetrachloride and methanol
A tetrasilabicyclo[1.1.0]but-1(3)-ene was synthesized as orange crystals and its reactions were investigated.
Dalton Trans., 2019,48, 10874-10880
https://doi.org/10.1039/C9DT01627A
Reversible borohydride formation from aluminium hydrides and {H(9-BBN)}2: structural, thermodynamic and reactivity studies
Aluminium borohydrides of the type (Nacnac)Al(R){H2(9-BBN)} are characterized by borane dissociation in solution under ambient conditions. This behaviour is critical to the ability of such complexes to reduce CO2.
Dalton Trans., 2019,48, 10845-10852
https://doi.org/10.1039/C9DT00535H
Reactivity of a gold(I)/platinum(0) frustrated Lewis pair with germanium and tin dihalides
The rich reactivity of tetrylene dihalides towards a metallic FLP: phosphine exchange reactions and formation of homo and heterobimetallic compounds.
Dalton Trans., 2019,48, 9127-9138
https://doi.org/10.1039/C9DT00702D
Reaction of an N/Al FLP-based aluminum hydride toward alkynes: deprotonated alumination versus hydroalumination with regioselective cis-addition character
The reactions of an N/Al FLP-based aluminum hydride with a terminal alkyne yielded the deprotonated alumination compound, while that with an internal alkyne yielded a hydroalumination product.
Dalton Trans., 2019,48, 9152-9160
https://doi.org/10.1039/C9DT00903E
Aluminium(III) dialkyl 2,6-bisimino-4R-dihydropyridinates(−1): selective synthesis, structure and controlled dimerization
2,6-Bisimino-4-alkyl-1,4-dihydropyridines provide access to dihydropyridinate(−1) aluminium(III) dialkyls, their double cycloaddition dimerization products and metal free ditopic ligands after controlled methanolysis.
Dalton Trans., 2019,48, 9104-9116
https://doi.org/10.1039/C9DT00847K
Computational studies of ene reactions between aminoborane (F3C)2BN(CH3)2 and substituted propenes: additive effects on barriers and reaction energies
Investigations of ene reactions between (F3C)2BNMe2 and substituted propenes reveal additive substitutional effects on barriers and reaction energies.
Dalton Trans., 2019,48, 8161-8174
https://doi.org/10.1039/C9DT01333D
Room temperature phosphorescent triarylborane functionalized iridium complexes
We report a series of room temperature phosphorescent compounds 1–6 composed of triarylborane (TAB) and cyclometallated iridium complexes.
Dalton Trans., 2019,48, 6817-6823
https://doi.org/10.1039/C9DT00590K
The impact of an isoreticular expansion strategy on the performance of iodine catalysts supported in multivariate zirconium and aluminum metal–organic frameworks
A new iodine catalyst was supported in two different MOFs and the catalytic activity for the oxidation of hydroquinones and catechols was evaluated.
Dalton Trans., 2019,48, 6445-6454
https://doi.org/10.1039/C9DT00368A
Heterobimetallic aluminate derivatives with bulky phenoxide ligands: a catalyst for selective vinyl polymerization
New aluminates as active catalysts for vinyl polymerization are described, as well as a strategy to crosslinked polymers from GMA in a controlled fashion.
Dalton Trans., 2019,48, 6435-6444
https://doi.org/10.1039/C9DT00761J
Phosphonate-assisted tetranuclear lanthanide assemblies: observation of the toroidic ground state in the TbIII analogue
Studies on [Ln4(LH2)2(O3PtBu)2(μ2-η1η1tfa)2]·2Cl (Ln = DyIII, TbIII and GdIII) reveal a SMM behaviour for the DyIII analogue and a SMT behaviour for the TbIII analogue.
Dalton Trans., 2019,48, 6421-6434
https://doi.org/10.1039/C9DT00592G
Reactivity patterns for the activation of CO2 and CS2 with alumoxane and aluminum hydrides
Alumoxane and aluminum dihydrides activate CO2 producing unusual inorganic cores while reactions with CS2 produce cyclic alumoxane and aluminum sulfides.
Dalton Trans., 2019,48, 5595-5603
https://doi.org/10.1039/C9DT00515C
Tellurorhodamine photocatalyzed aerobic oxidation of organo-silanes and phosphines by visible-light
Silanes and phosphines are photocatalytically oxidized with a self-sensitized tellurorhodamine under aerobic conditions.
Dalton Trans., 2019,48, 5665-5673
https://doi.org/10.1039/C9DT00487D
Reactivity of an NHC-stabilized pyramidal hydrosilylene with electrophilic boron sources
An NHC-stabilized three-coordinate hydrosilylene dehydrogenates ammonia borane and forms more stable complexes with BH3, BPh3, BBr3 and BPhBr2 but less stable ones with BF3, and BCl3 for which ligand scrambling occurs.
Dalton Trans., 2019,48, 5756-5765
https://doi.org/10.1039/C9DT00608G
Synthesis, characterization and biological evaluation of new manganese metal carbonyl compounds that contain sulfur and selenium ligands as a promising new class of CORMs
Three new manganese carbonyl compounds with heavy atom donors were synthesized and their potential use as photoCORMS was evaluated.
Dalton Trans., 2019,48, 5574-5584
https://doi.org/10.1039/C9DT00616H
Deprotonation, insertion and isomerisation in the post-functionalisation of tris-pyridyl aluminates
Reactions of aluminate anions [EtAl(6-R-2-py)3]−(6-R-2-py = 6-R-2-pyridyl, R = Me or Br) with aldehydes (RCHO) or carboxylic acids (RCO2H) reveal how these species can be used to sense chirality and show a new aspect of isomerism in this area.
Dalton Trans., 2019,48, 5692-5697
https://doi.org/10.1039/C9DT00869A
A phenalenyl-based nickel catalyst for the hydroboration of olefins under ambient conditions
Catalytic hydroboration of alkenes is reported using the redox active phenalenyl ligand assisted nickel complex Ni(PLY)2(THF)2 in the presence of pinacolborane under ambient conditions.
Dalton Trans., 2019,48, 5779-5784
https://doi.org/10.1039/C9DT00468H
Facile synthesis of mixed O, S or Se bearing hexasubstituted benzenes and their potential as Cu(II) ion probe
The synthesis of mixed hexasubstituted benzenes bearing alternate heteroatoms (O, S and Se) is described. The potential of these species as “turn-off” chemical sensors for Cu2+, which is a biologically and environmentally crucial metal ion, is also successfully demonstrated.
Dalton Trans., 2019,48, 5627-5636
https://doi.org/10.1039/C9DT00465C
Transmetallation of bis(6-diphenylphosphinoxy-acenapth-5-yl)mercury with tin tetrachloride, antimony trichloride and bismuth trichloride
The synthesis and structure of well-defined arylelement chlorides RSnCl4, RSnCl3·THF, RSbCl2, RSbCl2·THF and RBiCl2 is reported (R = 6-diphenylphosphinoxy-acenapth-5-yl).
Dalton Trans., 2019,48, 5585-5594
https://doi.org/10.1039/C9DT00827F
Evaluation of attractive interactions in the second coordination sphere of iron complexes containing pendant amines
The ability of different ligands to attract a pendant amine is studied in a series of iron complexes.
Dalton Trans., 2019,48, 4867-4878
https://doi.org/10.1039/C9DT00708C
Macrocyclic complexes of Pt(II) and Rh(III) with iso-tellurazole N-oxides
Tetramers of iso-tellurazole N-oxides form stable macrocyclic complexes with Pt(II) and Rh(III) in solution.
Dalton Trans., 2019,48, 4879-4886
https://doi.org/10.1039/C9DT00500E
Mononuclear lanthanide complexes assembled from a tridentate NNO donor ligand: design of a DyIII single-ion magnet
A new family of mononuclear LnIII complexes were synthesized by utilizing a tridentate Schiff base ligand. SIM behaviour is seen in the DyIII analogue (diluted) with Ueff = 68(2) K under a 1000 Oe applied dc field.
Dalton Trans., 2019,48, 4857-4866
https://doi.org/10.1039/C9DT00504H
Consecutive intermolecular 1,1-carboboration reactions of Me3Si-substituted alkynes with the halogeno-B(C6F5)2 reagents
1-(Trimethylsilyl)propyne 2a reacts with halogenoboranes XB(C6F5)2 (X: Cl, Br) in a 2 : 1 molar ratio under mild conditions by consecutive 1,1-carboboration reactions to give the highly substituted boryldienes 4.
Dalton Trans., 2019,48, 4837-4845
https://doi.org/10.1039/C9DT00413K
Alkylammoniotrifluoroborate functionalized polystyrenes: polymeric pre-catalysts for the metal-free borylation of heteroarenes
The synthesis and activity of the first polymeric frustrated Lewis pairs for the borylation of heteroarenes is reported.
Dalton Trans., 2019,48, 4846-4856
https://doi.org/10.1039/C9DT00484J
Salen supported Al–O–CP and Ga–PCO complexes
The synthesis and reactivity of salen supported OCP adducts of aluminium and gallium is reported.
Dalton Trans., 2019,48, 4370-4374
https://doi.org/10.1039/C9DT00485H
Synthesis of helical aluminium catalysts for cyclic carbonate formation
Helical aluminium complexes have been prepared and used as catalysts for cyclic carbonate synthesis.
Dalton Trans., 2019,48, 4218-4227
https://doi.org/10.1039/C9DT00323A
Chalcogen stabilized trimetallic clusters: synthesis, structures, and bonding of [(Cp*M)3(E)6+m(BH)n] (M = Nb or Ta; E = S or Se; m = 0 or 1 or 2; n = 0 or 1)
An unusual trimetallic octaselenide complex, [(Cp*Ta)3(μ-Se)4{μ-Se2(Se2)}], has been synthesized and structurally characterized.
Dalton Trans., 2019,48, 4203-4210
https://doi.org/10.1039/C8DT05061A
Selective reduction of formamides to O-silylated hemiaminals or methylamines with HSiMe2Ph catalyzed by iridium complexes
Ir–NSitBu based catalysts allow the control of the selective reduction of formamides with HSiMe2Ph to afford O-silylated hemiaminals or methylamines.
Dalton Trans., 2019,48, 4255-4262
https://doi.org/10.1039/C8DT05070H
Isolation of ligand-centered borocations in molybdenum complexes containing a triaminoborane-bridged diphosphorus ligand
Metal complexes that form isolable, ligand-centered borenium ions (i.e. reactive three-coordinate boron cations) are rare, especially with highly-versatile diphosphorus ligands.
Dalton Trans., 2019,48, 3777-3785
https://doi.org/10.1039/C9DT00733D
Increasing steric demand through flexible bulk – primary phosphanes with 2,6-bis(benzhydryl)phenyl backbones
Novel primary phosphanes with bulky 2,6-bis(benzhydryl)phenyl substituents could be prepared and fully characterized.
Dalton Trans., 2019,48, 3786-3794
https://doi.org/10.1039/C9DT00399A
Dinuclear organogermanium chalcogenide complexes as intermediates towards functionalized clusters
Compounds [(R1GeCl)2E2] were isolated upon reactions of R1GeCl3 (R1 = CMe2CH2COMe) with (Me3Si)2E (E = S, Se, Te) as intermediates of the [(R1Ge)4E6] cluster formation.
Dalton Trans., 2019,48, 3671-3675
https://doi.org/10.1039/C9DT00310J
Catechol and 1,2,4,5-tetrahydroxybenzene functionalized cyclodiphosphazane ligands: synthesis, structural studies, and transition metal complexes
This paper describes the syntheses of two novel cyclodiphosphazane derivatives and their coordination chemistry with CuI, RuII, RhI, PdII and AuI is also described.
Dalton Trans., 2019,48, 3610-3624
https://doi.org/10.1039/C8DT04819C
Cooperative activation of O–H and S–H bonds across the Co–P bond of an N-heterocyclic phosphido complex
A cobalt N-heterocyclic phosphido complex is shown to cleave element–hydrogen bonds via a metal–phosphorus ligand cooperative pathway.
Dalton Trans., 2019,48, 3074-3079
https://doi.org/10.1039/C8DT05052J
A series of new vanadium(III) chalcogenido-antimonates: an unusual seven-coordinate nitro-selenidovanadium(III) complex
This work provides a rare example of high coordination of a nitro-selenidovanadium(III) complex with photocurrent response properties.
Dalton Trans., 2019,48, 3090-3097
https://doi.org/10.1039/C9DT00268E
Anionic and neutral 2D indium metal–organic frameworks as catalysts for the Ugi one-pot multicomponent reaction
Two metal–organic frameworks (MOFs) made of indium and 1,3,5-tris(4-carboxyphenyl)benzene and having a layered structure have been synthesized, showing catalytic activity in the one-pot Ugi reaction.
Dalton Trans., 2019,48, 2988-2995
https://doi.org/10.1039/C8DT04977G
Enhanced CO2 capture by reducing cation–anion interactions in hydroxyl-pyridine anion-based ionic liquids
An efficient strategy for enhancing CO2 capture performance based on 2-hydroxyl pyridium anion-functionalized ILs was reported via the reduction of cation–anion interactions in ILs.
Dalton Trans., 2019,48, 2300-2307
https://doi.org/10.1039/C8DT04680H
Simultaneous expansion of 9,10 boron-doped anthracene in longitudinal and lateral directions
Key structural and optoelectronic features of 2,3,6,7-tetraarylated diboraanthracenes were compared with those of corresponding singly and doubly ring-closed diboratetracenes and -pentacenes.
Dalton Trans., 2019,48, 1871-1877
https://doi.org/10.1039/C8DT04820G
Tetrazastannoles versus distannadiazanes – a question of the tin(II) source
Depending on the Sn(II) compound used, reactions with two equivalents of azide led to the formation of tetrazastanols [R2N4SnR′2] or cyclo-distannadiazanes [R2Sn(μ-NR′)]2.
Dalton Trans., 2019,48, 125-132
https://doi.org/10.1039/C8DT04295K
Design considerations for chiral frustrated Lewis pairs: B/N FLPs derived from 3,5-bicyclic aryl piperidines
3,5-Bicyclic aryl piperidines are derivatized to generate chiral B/N FLPs. The Lewis acidities were assessed by experimental and computational methods. The activity in HD scrambling and hydrogenation was also assessed. These data demonstrate that a threshold of combined Lewis acidity and basicity is essential to activate H2.
Dalton Trans., 2019,48, 133-141
https://doi.org/10.1039/C8DT04070B
Modifying methylalumoxane via alkyl exchange
Ionized methylalumoxane exchanges alkyl groups rapidly with trialkylaluminums in solution, generating statistical mixtures of modified methylalumoxane anions.
Dalton Trans., 2018,47, 17291-17298
https://doi.org/10.1039/C8DT04242J
About this collection
This web-theme special issue of Dalton Transactions focuses on the inorganic chemistry of the p-block elements, as a tribute to the 150th anniversary of the development of the periodic table. Guest edited by Zachariah M. Heiden (Washington State University), Marta E. G. Mosquera (Alcalá University), and Harkesh B. Singh (Indian Institute of Technology, Bombay), this collection of more than 40 reports on the chemistry of p-block elements, encompasses five of the six p-block families, and 18 of the 31 p-block elements. The large contribution and breadth of reports included in this special issue is evidence of an increasing interest in this field, and confirms that the future of the chemistry of the p-block elements is bright.