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Themed collection Philip Power at 65: an icon of organometallic chemistry

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Editorial

Philip Power at 65: an icon of organometallic chemistry

We are delighted to present this collection of articles to celebrate the work of Philip Power on the occasion of his 65th birthday.

Graphical abstract: Philip Power at 65: an icon of organometallic chemistry
Perspective

Multidentate silyl ligands in transition metal chemistry

This review presents and discusses the use of multidentate silanide ligands in transition metal chemistry depending on their ligand architecture.

Graphical abstract: Multidentate silyl ligands in transition metal chemistry
Perspective

Recent developments in the chemistry of low valent Group 14 hydrides

This Perspective discusses the synthesis and reactivity of low valent germanium and tin hydrides. The use of hindered terphenyl ligands has led to the isolation of a number of unusual structure types (each predicted by theory), and has culminated in their use as precursors to new cluster archetypes.

Graphical abstract: Recent developments in the chemistry of low valent Group 14 hydrides
Frontier

Understanding the origins of Oyl–U–Oyl bending in the uranyl (UO22+) ion

Although rare, Oyl–U–Oyl bending in the uranyl (UO22+) ion can be effected by either steric perturbation or electronic perturbation.

Graphical abstract: Understanding the origins of Oyl–U–Oyl bending in the uranyl (UO22+) ion
From the themed collection: 2018 Frontier and Perspective articles
Feature Article

Silicon chemistry in zero to three dimensions: from dichlorosilylene to silafullerane

As one of the simplest examples of functionalized Si(II) species, the SiCl2/[SiCl3] system is not only fundamentally interesting, but also an important starting point for the assembly of oligosilane chains, rings, and clusters.

Graphical abstract: Silicon chemistry in zero to three dimensions: from dichlorosilylene to silafullerane
Feature Article

Silicon, germanium, tin and lead analogues of acetylenes

Current work on the synthesis, characterization and bonding in the heavier group 14 element (Si–Pb) analogues of alkynes is described and discussed.

Graphical abstract: Silicon, germanium, tin and lead analogues of acetylenes
Review Article

Complexes of Ni(I): a “rare” oxidation state of growing importance

The synthesis and diverse structures, reactivity (small molecule activation and catalysis) and magnetic properties of Ni(I) complexes are summarized.

Graphical abstract: Complexes of Ni(i): a “rare” oxidation state of growing importance
Communication

Mono- and dinuclear tetraphosphabutadiene ferrate anions

Anionic tetraphosphido complexes are accessible by reacting white phosphorus with low-valent cyclopentadienyliron species prepared by alkali metal reduction (Ar = C6H4-4-Et, 18-c-6 = [18]crown-6).

Graphical abstract: Mono- and dinuclear tetraphosphabutadiene ferrate anions
Open Access Communication

A diarsagermylene and a diarsastannylene stabilised by arene⋯Ge/Sn interactions

Unusual arene⋯Ge/Sn interactions stabilise the rare diarsatetrylenes 8Ge/Sn by up to 181 kJ mol−1.

Graphical abstract: A diarsagermylene and a diarsastannylene stabilised by arene⋯Ge/Sn interactions
Communication

Arrested disproportionation in trivalent, mononuclear, and non-metallocene complexes of Zr(III) and Hf(III)

Reduction of [(PN)2MCl2] (M = Zr (1), and Hf (2)) both readily prepared by transmetallation of 2 LiPN with [MCl4(THF)2], with a slight excess of KC8, resulted in the isolation of the trivalent complexes [(PN)2MCl] (M = Zr (3), and Hf (4)).

Graphical abstract: Arrested disproportionation in trivalent, mononuclear, and non-metallocene complexes of Zr(iii) and Hf(iii)
Communication

Dehydrogenation of dimethylamine-borane mediated by Group 1 pincer complexes

Alkali metal carbazolido complexes are precatalysts for the dehydrogenation of Me2NH·BH3, where the cation plays a vital role in the reaction outcome.

Graphical abstract: Dehydrogenation of dimethylamine-borane mediated by Group 1 pincer complexes
Communication

An isolable β-diketiminato chlorosilylene

The first β-diketiminate ligated chlorosilylene has been synthesised and isolated from the corresponding β-diketiminato dichlorohydrosilane through dehydrochlorination with an N-heterocyclic carbene.

Graphical abstract: An isolable β-diketiminato chlorosilylene
Communication

Catalytic N–Si coupling as a vehicle for silane dehydrocoupling via α-silylene elimination

Zirconium compounds appear to promote the liberation of silylene fragments via an N–Si coupling event.

Graphical abstract: Catalytic N–Si coupling as a vehicle for silane dehydrocoupling via α-silylene elimination
Communication

Dialumination of unsaturated species with a reactive bis(cyclopentadienyl) dialane

A new cyclopentadienyl-containing dialane is prepared and found to undergo dialumination reactions with unsaturated species.

Graphical abstract: Dialumination of unsaturated species with a reactive bis(cyclopentadienyl) dialane
Communication

Syntheses, structures and theoretical calculations of stable triarylarsine radical cations

Two stable triarylarsine radical cation salts have been synthesized and fully characterized by X-ray crystallography and EPR spectroscopy.

Graphical abstract: Syntheses, structures and theoretical calculations of stable triarylarsine radical cations
Communication

(Ge2P2)2−: a binary analogue of P4 as a precursor to the ternary cluster anion [Cd3(Ge3P)3]3−

The novel binary P4 analogue (Ge2P2)2− proved to be a suitable precursor for heteroatomic cluster synthesis. Upon reaction with CdPh2, an unprecedented cluster anion is formed, [Cd3(Ge3P)3].

Graphical abstract: (Ge2P2)2−: a binary analogue of P4 as a precursor to the ternary cluster anion [Cd3(Ge3P)3]3−
Open Access Communication

Lithium diamidodihydridoaluminates: bimetallic cooperativity in catalytic hydroboration and metallation applications

Cooperativity between the Li and Al centres is implicated in catalytic hydroboration reactions of aldehydes and ketones with pinacolborane via heteroleptic lithium diamidodihydridoaluminates.

Graphical abstract: Lithium diamidodihydridoaluminates: bimetallic cooperativity in catalytic hydroboration and metallation applications
Communication

Catalytic oxidative coupling promoted by bismuth TEMPOxide complexes

Bismuth(III) TEMPOxide complexes are active catalysts for oxidative coupling reactions to generate TEMPO silylethers.

Graphical abstract: Catalytic oxidative coupling promoted by bismuth TEMPOxide complexes
Open Access Communication

Neutral two-dimensional organometallic–organic hybrid polymers based on pentaphosphaferrocene, bipyridyl linkers and CuCl

The reaction of the Pn ligand complex [Cp*Fe(η5-P5)] (1: Cp* = η5-C5Me5) with CuCl in the presence of 4,4′-bipyridine or 1,2-di(4-pyridyl)ethylene leads to the formation of three unprecedented neutral 2D organometallic–organic hybrid networks.

Graphical abstract: Neutral two-dimensional organometallic–organic hybrid polymers based on pentaphosphaferrocene, bipyridyl linkers and CuCl
Communication

Approaching monocoordination at a silver(I) cation

A series of highly electrophilic [(NHC)Ag]+ complexes (NHC = N-heterocyclic carbene) have been prepared which approach the limit of monocoordination for silver(I).

Graphical abstract: Approaching monocoordination at a silver(i) cation
Communication

Reversible addition of terminal alkenes to digermynes

Stable digermynes with sterically demanding Bbt (Bbt = 2,6-[CH(SiMe3)2]2-4-[C(SiMe3)3]-C6H2) or Tbb (Tbb = 4-tBu-2,6-[CH(SiMe3)2]2-C6H2) groups underwent reversible [2+2] cycloadditions with terminal alkenes to give the corresponding 1,2-digermacyclobutenes.

Graphical abstract: Reversible addition of terminal alkenes to digermynes
Communication

Carbodiimides as catalysts for the reduction of a cadmium hydride complex

A rare terminal cadmium hydride complex has been synthesised. Reduction to the cadmium(I) dimer complex was achieved upon treatment with carbodiimides.

Graphical abstract: Carbodiimides as catalysts for the reduction of a cadmium hydride complex
Open Access Communication

Aluminium-mediated carbon–carbon coupling of an isonitrile

Cp*Al reacts with diphenylacetylene to form a Cp*-substituted 1,4-dialuminacyclohexene, which mediates the coupling of isonitriles to form a new zwitterionic diamide ligand with a carbocationic backbone.

Graphical abstract: Aluminium-mediated carbon–carbon coupling of an isonitrile
Communication

1,3,2-Diazaborole-derived carbene complexes of boron

1,3,2-Diazaborole-derived carbene complexes of boron were synthesized via 1,2-hydrogen migration.

Graphical abstract: 1,3,2-Diazaborole-derived carbene complexes of boron
Communication

An ambiphilic phosphine/H-bond donor ligand and its application to the gold mediated cyclization of propargylamides

We describe the synthesis of an ambiphilic phosphine/H-bond donor ligand featuring a trifluoroacetamide functionality, its coordination to gold(I) chloride, and its application as a self-activating catalyst for the cyclization of propargylamides.

Graphical abstract: An ambiphilic phosphine/H-bond donor ligand and its application to the gold mediated cyclization of propargylamides
Open Access Communication

C–H and H–H activation at a di-titanium centre

An NHC promotes intramolecular C–H activation in bis(pentalene)dititanium; this process is reversed by the addition of hydrogen, forming a dihydride.

Graphical abstract: C–H and H–H activation at a di-titanium centre
Open Access Communication

Synthesis of new hybrid 1,4-thiazinyl-1,2,3-dithiazolyl radicals via Smiles rearrangement

New hybrid 1,4-thiazine-1,2,3-dithiazolylium salts were prepared via Smiles rearrangement. The cations can be readily reduced to the corresponding stable neutral radicals with delocalised spin densities.

Graphical abstract: Synthesis of new hybrid 1,4-thiazinyl-1,2,3-dithiazolyl radicals via Smiles rearrangement
Communication

Chalcogen-atom transfer and exchange reactions of NHC-stabilized heavier silaacylium ions

Facile access to heavier silaacylium ions stabilized by two NHCs and their chalcogen transfer and exchange reactivity are reported.

Graphical abstract: Chalcogen-atom transfer and exchange reactions of NHC-stabilized heavier silaacylium ions
Communication

A snapshot of inorganic Janovsky complex analogues featuring a nucleophilic boron center

The addition of phenyl lithium (PhLi) to an aromatic 1,3,2,5-diazadiborinine (1) afforded isolable ionic species 2, which can be deemed as an inorganic analogue of a Janovsky complex.

Graphical abstract: A snapshot of inorganic Janovsky complex analogues featuring a nucleophilic boron center
Communication

Alkylideneborate zwitterions and C–C coupling by atypical diboration of electron-rich alkynes

The combination of electron-rich diaminoalkynes and ditopic Lewis acids diboranes(4) leads to unusual diboration reactions involving internal Lewis adduct and zwitterion formation and C–C bond formation.

Graphical abstract: Alkylideneborate zwitterions and C–C coupling by atypical diboration of electron-rich alkynes
Communication

Dinuclear zinc(II) pyrazolates with different degrees of ring-fluorination and their use in zinc(II) mediated olefin aziridination

A highly fluorinated pyrazolate complex of zinc has been isolated and utilized as a competent catalyst for olefin aziridination.

Graphical abstract: Dinuclear zinc(ii) pyrazolates with different degrees of ring-fluorination and their use in zinc(ii) mediated olefin aziridination
Communication

Efficient and selective catalysis for hydrogenation and hydrosilation of alkenes and alkynes with PNP complexes of scandium and yttrium

Scandium and yttrium congeneric complexes, supported by a monoanionic PNP ligand, were studied as catalysts for alkene hydrogenation and hydrosilation and alkyne semihydrogenation and semihydrosilation.

Graphical abstract: Efficient and selective catalysis for hydrogenation and hydrosilation of alkenes and alkynes with PNP complexes of scandium and yttrium
Communication

[Hyp-Au-Sn9(Hyp)3-Au-Sn9(Hyp)3-Au-Hyp]: the longest intermetalloid chain compound of tin

The reaction of the metalloid tin cluster [Sn10(Hyp)4]2− with (Ph3P)Au-SHyp (Hyp = Si(SiMe3)3) gave an intermetalloid cluster [Au3Sn18(Hyp)8]1, which is the longest intermetalloid chain compound of tin to date.

Graphical abstract: [Hyp-Au-Sn9(Hyp)3-Au-Sn9(Hyp)3-Au-Hyp]−: the longest intermetalloid chain compound of tin
Communication

Synthesis and characterization of Lewis base stabilized mono- and di-organo aluminum radicals

Synthesis, structure, EPR and theoretical calculations of cyclic (alkyl)(amino)carbene stabilized mononuclear neutral radicals of aluminum containing mono- and di-organo groups.

Graphical abstract: Synthesis and characterization of Lewis base stabilized mono- and di-organo aluminum radicals
Communication

Targeted attachment of functional groups at Ge9 clusters via silylation reactions

A metalloid Ge clusters receives reactive substituents.

Graphical abstract: Targeted attachment of functional groups at Ge9 clusters via silylation reactions
Communication

Stoichiometric and catalytic isomerization of alkenylboranes using bulky Lewis bases

Mixtures of E and Z isomers of alkenylboranes are isomerized upon treatment with stoichiometric or catalytic amounts of tBu2PH or other donors.

Graphical abstract: Stoichiometric and catalytic isomerization of alkenylboranes using bulky Lewis bases
Communication

Catalytic dehydrocoupling of amines and boranes by an incipient tin(II) hydride

{ArMe6Sn(μ-OMe)}2 (1, ArMe6 = C6H3-2,6-(C6H2-2,4,6-Me3)2) and {AriPr4Sn(μ-OMe)}2 (2, AriPr4 = C6H3-2,6-(C6H3-2,6-iPr2)2) facilitate the dehydrocoupling of ammonia, 1° and 2° amines with HBpin. 2 catalyzes the reactions faster than 1 but is limited to 1° amines. Synthesis and characterization of a tin(II) amide and amide-hydride give insight into the catalytic mechanism.

Graphical abstract: Catalytic dehydrocoupling of amines and boranes by an incipient tin(ii) hydride
Communication

Activation of olefins with low-valent gallium compounds under ambient conditions

The reactions of Ar′GaGaAr′ with alkenes revealed the addition of two olefins per Ar′GaGaAr′ under ambient conditions with ethylene, propene, 1-hexene or styrene but no addition for more hindered or cyclic olefins.

Graphical abstract: Activation of olefins with low-valent gallium compounds under ambient conditions
Communication

Unusual magnetic properties of a two-coordinate heteroleptic linear cobalt(II) complex

The first linearly coordinated heteroleptic cobalt(II) species Ar′CoN(SiMe3)2 shows an unexpectedly large effective magnetic moment.

Graphical abstract: Unusual magnetic properties of a two-coordinate heteroleptic linear cobalt(ii) complex
Communication

Insertion reactions of a two-coordinate iron diaryl with dioxygen and carbon monoxide

The iron(II) diaryl FeAr′2 (1) reacts cleanly with O2 or CO to afford the monomeric, two-coordinate bis(aryloxide) Fe(OAr′)2 (2) or the acyl–carbonyl complex (η2-Ar′C[double bond, length as m-dash]O)2Fe(CO)2 (3) via oxygen atom or CO insertion into the Fe–C bonds. Complex 2 has a strictly linear geometry and shows remarkable resistance to O2 oxidation.

Graphical abstract: Insertion reactions of a two-coordinate iron diaryl with dioxygen and carbon monoxide
Communication

Reactions of Ar′CrCrAr′ with N2O or N3(1-Ad): complete cleavage of the Cr–Cr quintuple interaction

The reaction of Ar′CrCrAr′ with N2O or N3(1-Ad) under mild conditions leads to complete cleavage of the Cr–Cr quintuple interaction.

Graphical abstract: Reactions of Ar′CrCrAr′ with N2O or N3(1-Ad): complete cleavage of the Cr–Cr quintuple interaction
Communication

Addition of H2 to distannynes under ambient conditions

H2 reacts with a series of distannynes at ca. 25 °C and 1 atmosphere pressure to give Sn2H2Ar2 products whose structures depend on the type of terphenyl ligand employed.

Graphical abstract: Addition of H2 to distannynes under ambient conditions
Communication

Univalent transition metal complexes of arenes stabilized by a bulky terphenyl ligand: differences in the stability of Cr(I), Mn(I) or Fe(I) complexes

Unlike their Cr(I) counterpart, the arene complexes of the univalent MAr moieties (M = Mn or Fe, Ar = terphenyl) are stable under ambient conditions.

Graphical abstract: Univalent transition metal complexes of arenes stabilized by a bulky terphenyl ligand: differences in the stability of Cr(i), Mn(i) or Fe(i) complexes
Communication

Convergent syntheses of [Sn7{C6H3-2,6-(C6H3-2,6-iPr2)2}2]: a cluster with a rare pentagonal bipyramidal motif

Two complementary routes to an unusual pentagonal bipyramidal cluster, Sn5(SnAr′)2 (Ar′ = terphenyl ligand), are reported.

Graphical abstract: Convergent syntheses of [Sn7{C6H3-2,6-(C6H3-2,6-iPr2)2}2]: a cluster with a rare pentagonal bipyramidal motif
Communication

Different reactivity of the heavier group 14 element alkyne analogues Ar′MMAr′ (M = Ge, Sn; Ar′ = C6H3-2,6(C6H3-2,6-Pri2)2) with R2NO

The reactions of the digermanium and ditin alkyne analogues Ar′MMAr′ (M = Ge or Sn) with R2NO, (R2NO = Me2C[upper bond 1 start](CH2)3CMe2N[upper bond 1 end]O or N2O), result in complete MM bond cleavage to afford the germylene :Ge(Ar′)ONR2 or the germanium(II) or tin(II) hydroxides {M(Ar′)(μ–OH)}2.

Graphical abstract: Different reactivity of the heavier group 14 element alkyne analogues Ar′MMAr′ (M = Ge, Sn; Ar′ = C6H3-2,6(C6H3-2,6-Pri2)2) with R2NO
Communication

Formation of [Ar*Ge[upper bond 1 start]{CH2C(Me)C(Me)C[upper bond 1 end]H2}CH2C(Me)[double bond, length as m-dash]]2 (Ar* = C6H3-2,6-Trip2; Trip = C6H2-2,4,6-i-Pr3) via reaction of Ar*GeGeAr* with 2,3-dimethyl-1,3-butadiene: evidence for the existence of a germanium analogue of an alkyne

The reduction of Ar*GeCl with one equivalent of potassium affords a germanium analogue of an alkyne Ar*GeGeAr* which reacts with dimethyl-1,3-butadiene to yield the structurally characterized compound [Ar*Ge[upper bond 1 start]{CH2C(Me)C(Me)C[upper bond 1 end]H2}CH2C(Me)[double bond, length as m-dash]]22, illustrated opposite.

Graphical abstract: Formation of [Ar*Ge [[upper bond 1 start]] {CH2C(Me)C(Me)C [[upper bond 1 end]] H2}CH2C(Me) [[double bond, length as m-dash]] ]2 (Ar* = C6H3-2,6-Trip2; Trip = C6H2-2,4,6-i-Pr3) via reaction of Ar*GeGeAr* with 2,3-dimethyl-1,3-butadiene: evidence for the existence of a germanium analogue of an alkyne
Communication

Persistent phosphinyl radicals from a bulky diphosphine: an example of a molecular jack-in-the-box

Communication

Synthesis and characterization of the monomer Ga{(NDippCMe)2CH} (Dipp = C6H3Pri2-2,6): a low valent gallium(I) carbene analogue

Open Access Edge Article

The multiple bonding in heavier group 14 element alkene analogues is stabilized mainly by dispersion force effects

Computations on the heavier group 14 dimetallenes [E{CH(SiMe3)2}2]2 and [E{N(SiMe3)2}2]2 (E = Ge, Sn, or Pb) and their respective monomers indicated that empirically observed dimerization is principally driven by attractive dispersion forces.

Graphical abstract: The multiple bonding in heavier group 14 element alkene analogues is stabilized mainly by dispersion force effects
Edge Article

Slow magnetization dynamics in a series of two-coordinate iron(II) complexes

The magnetic properties of two-coordinate complexes of iron(II) were analyzed to explore their utility as single-molecule magnets.

Graphical abstract: Slow magnetization dynamics in a series of two-coordinate iron(ii) complexes
Edge Article

Substituent effects in ditetrel alkyne analogues: multiple vs. single bonded isomers

The synthesis and characterization of a series of digermynes and distannynes stabilized by terphenyl ligands are described. The findings are in agreement with calculations that show that there is little energy difference between the multiple and singly bonded forms of distannynes.

Graphical abstract: Substituent effects in ditetrel alkyne analogues: multiple vs. single bonded isomers
Paper

Heterobimetallic triple-decker complexes derived from a dianionic aromatic stannole ligand

A neutral heterobimetallic triple-decker stannole complex was prepared by the reaction of an anionic ruthenocene bearing a stannole dianionic ligand with [Rh(cod)Cl]2 (cod = 1,5-cyclooctadiene), and the resulting Ru–Rh complex exhibits an electronic property different from those of the corresponding Ru–Ru and Rh–Rh complexes.

Graphical abstract: Heterobimetallic triple-decker complexes derived from a dianionic aromatic stannole ligand
Open Access Paper

Synthesis, characterisation and thermal properties of Sn(II) pyrrolide complexes

A series of Sn(II) pyrrolide complexes have been synthesised, characterised and their thermal properties assessed for their potential application in the MOCVD and ALD of SnO thin films.

Graphical abstract: Synthesis, characterisation and thermal properties of Sn(ii) pyrrolide complexes
Paper

Dispersion forces play a role in (Me2IPr)Fe([double bond, length as m-dash]NAd)R2 (Ad = adamantyl; R = neoPe, 1-nor) insertions and Fe–R bond dissociation enthalpies (BDEs)

Calculations show that dispersion forces in four-coordinate (Me2IPr)Fe([double bond, length as m-dash]NAd)(1-nor)2 (2b) contribute to greater D(FeR) and subtly slow its migratory insertion relative to the neopentyl analogue.

Graphical abstract: Dispersion forces play a role in (Me2IPr)Fe( [[double bond, length as m-dash]] NAd)R2 (Ad = adamantyl; R = neoPe, 1-nor) insertions and Fe–R bond dissociation enthalpies (BDEs)
Open Access Paper

Spirocyclic germanes via transannular insertion reactions of vinyl germylenes into Si–Si bonds

The reaction of cyclic disilylated germylene phosphane adducts with alkynes gives spirocyclic germanes via the intermediate formation of cyclic divinylgermylenes.

Graphical abstract: Spirocyclic germanes via transannular insertion reactions of vinyl germylenes into Si–Si bonds
Paper

Neutral and anionic zinc compounds supported by a bis(imino)phenyl NCN ligand

The new zinc complexes 2,6-(ArN[double bond, length as m-dash]CH)2C6H3ZnBu (6) and 2,6-(ArN[double bond, length as m-dash]CH)2C6H3ZnCl2Li(THF)3 (7), supported by a bis(imino)phenyl NCN pincer ligand, were prepared (Ar = 2,6-iPr2C6H3).

Graphical abstract: Neutral and anionic zinc compounds supported by a bis(imino)phenyl NCN ligand
Paper

Boron calixphyrin complexes: exploring the coordination chemistry of a BODIPY/porphyrin hybrid

Calix[4]phyrin (1,1,1,1) proves to be a versatile ligand for boron with both mono- and di-boron complexes exhibiting unusual regio- and stereoisomerism.

Graphical abstract: Boron calixphyrin complexes: exploring the coordination chemistry of a BODIPY/porphyrin hybrid
Paper

A utility for organoleads: selective alkyl and aryl group transfer to tin

Me4Pb and Ph4Pb readily transfer methyl or phenyl groups to an equivalent molar ratio of tin(IV) chlorides in the order SnCl4 > MeSnCl3 > Me2SnCl2 > Me3SnCl, often in a selective manner.

Graphical abstract: A utility for organoleads: selective alkyl and aryl group transfer to tin
Paper

Frustrated Lewis pairs incorporating the bifunctional Lewis acid 1,1′-fc{B(C6F5)2}2: reactivity towards small molecules

Applications of the bifunctional Lewis acid 1,1′-fc{B(C6F5)2}2 in FLP chemistry are described, including reactions towards H2O, NH3, CO2 and cyclohexylisocyanate.

Graphical abstract: Frustrated Lewis pairs incorporating the bifunctional Lewis acid 1,1′-fc{B(C6F5)2}2: reactivity towards small molecules
Paper

Divergent reactivity of nucleophilic 1-bora-7a-azaindenide anions

The reactions of 1-bora-7a-azaindenide anions, prepared in moderate to excellent yields by reduction of the appropriate 1-bora-7a-azaindenyl chlorides with KC8 in THF, with alkyl halides and carbon dioxide were studied.

Graphical abstract: Divergent reactivity of nucleophilic 1-bora-7a-azaindenide anions
Open Access Paper

Mono- and dinuclear Ni(I) products formed upon bromide abstraction from the Ni(I) ring-expanded NHC complex [Ni(6-Mes)(PPh3)Br]

New T- and Y-shaped Ni(I) complexes are reported and analysed by DFT and EPR.

Graphical abstract: Mono- and dinuclear Ni(i) products formed upon bromide abstraction from the Ni(i) ring-expanded NHC complex [Ni(6-Mes)(PPh3)Br]
Paper

Coordination chemistry of stannylene-based Lewis pairs – insertion into M–Cl and M–C bonds. From base stabilized stannylenes to bidentate ligands

The coordination chemistry of intramolecular stannylene phosphorus Lewis pairs incorporated into four or three membered ring molecules is presented.

Graphical abstract: Coordination chemistry of stannylene-based Lewis pairs – insertion into M–Cl and M–C bonds. From base stabilized stannylenes to bidentate ligands
Paper

Synthesis, spectroscopic characterisation and transmetalation of lithium and potassium diaminophosphanide-boranes

Deprotonation of a secondary diaminophosphane-borane yields lithium and potassium diaminophosphanide-boranes which undergo transmetalation to yield isolable Cu(I) and Zn(II) complexes.

Graphical abstract: Synthesis, spectroscopic characterisation and transmetalation of lithium and potassium diaminophosphanide-boranes
Paper

f-Block complexes of a m-terphenyl dithiocarboxylate ligand

Homoleptic thorium(IV), uranium(IV), and lanthanum(III) dithiocarboxylate complexes were prepared and studied electrochemically; the lanthanum complex was found to bind toluene.

Graphical abstract: f-Block complexes of a m-terphenyl dithiocarboxylate ligand
Paper

PNacPNacE: (E = Ga, In, Tl) – monomeric group 13 metal(I) heterocycles stabilized by a sterically demanding bis(iminophosphoranyl)methanide

Monomeric group 13 metal(I) complexes of gallium, indium and thallium stabilised by a sterically demanding bis(iminophosphoranyl)methanide ligand have been prepared and characterised.

Graphical abstract: PNacPNacE: (E = Ga, In, Tl) – monomeric group 13 metal(i) heterocycles stabilized by a sterically demanding bis(iminophosphoranyl)methanide
Paper

Accessing multimetallic complexes with a phosphorus(I) zwitterion

The synthesis of a zwitterionic triphosphenium molecule which acts as a multidentate donor with various zero-velent transition metal complexes is presented. These mono- and bimetallic complexes can either be bound through the P(I) center or through the cyclopentadienyl moiety on the backbone of the molecule.

Graphical abstract: Accessing multimetallic complexes with a phosphorus(i) zwitterion
Paper

Dicationic phosphonium salts: Lewis acid initiators for the Mukaiyama-aldol reaction

Two strategies were used to prepare dicationic phosphonium cations.

Graphical abstract: Dicationic phosphonium salts: Lewis acid initiators for the Mukaiyama-aldol reaction
Paper

Donor–acceptor interactions in tri(phosphonio)methanide dications [(Ph3P)2CP(X)Ph2]2+ (X = H, Me, CN, NCS, OH, Cl, OTf, F)

The impact of the strongly electron donating carbodiphosphorane moiety in the series of tri(phosphonio)methanide dications as triflate salts [(Ph3P)2CP(X)Ph2][OTf]2 (X = H, Me, CN, NCS, OH, Cl, OTf, F) deriving from [(Ph3P)2CPPh2][OTf] (19[OTf]) is presented.

Graphical abstract: Donor–acceptor interactions in tri(phosphonio)methanide dications [(Ph3P)2CP(X)Ph2]2+ (X = H, Me, CN, NCS, OH, Cl, OTf, F)
Paper

Reactivity of sulfonyl-containing compounds with ditetrelenes

Ditetrelenes selectively reduce sulfonyl chlorides to sulfinates.

Graphical abstract: Reactivity of sulfonyl-containing compounds with ditetrelenes
Paper

Unsymmetric dipnictenes—synthesis and characterization of MesP[double bond, length half m-dash]EC6H3-2,6-Trip2 (E = As or Sb; Mes = C6H2-2,4,6-Me3, Trip = C6H2-2,4,6-Pri3)

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About this collection

Professor Philip P. Power, an icon of organometallic chemistry, turns 65 in April 2018. Phil is a distinguished Professor of Inorganic Chemistry at the University of California, Davis. Having completed his BA (Chemistry) at Trinity College, Dublin in 1974, Phil received his PhD under Professor Michael F. Lappert, FRS in 1977. After this time, Phil worked as a postdoctoral researcher with Professor Richard H. Holm at Stanford, before taking up a position at Davis in 1981.

In honour of this anniversary, we have collected 27 of Phil’s contributions to RSC journals, and thank over 45 of his previous co-workers, and chemists whose work is allied to Phil’s for contributing original research to this special collection. These papers reflect Phil’s wide-ranging interests and propensity for timely research, as well as his provision of a range of useful and often field-defining reviews.

Since 1981, Phil has been the recipient of a plethora of awards, fellowships, prizes and honorary lectureships. His scientific excellence is beyond question, and working with Phil is a thoroughly enjoyable, if cerebrally challenging, experience. Phil’s lab has been a stepping stone in many chemist’s early career and he has had a dramatic impact on organometallic and inorganic chemistry. We have all worked with Phil either as postdoctoral fellows, or hosting him as a visiting professor and hope these papers, and our editorial, reflect his unique approach to science as well as his unique character.

These papers will be free-to-access for the next two months so please join us in celebrating the birthday of a titan of organometallic chemistry through some of the highlights of his career to date, and through the fantastic new research proffered by other researchers in the field.

Roland C. Fischer, Michael S. Hill and David J. Liptrot, April 2018

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