Molecules

Some of our recently published structures

 Our bis(cyaphido) complex, as an x-ray structure

 

[Ru(dppe)2(C≡P)2

Chem. Eur. J., 2024, e202303370

We recently reported the first example of a monometallic bis(cyaphido) complex.  Considered alongside our previously reported trans cyaphido-carbonyl, and a novel trans-cyano-cyaphide complex (see below), structural and computational data substantiated previous assertion of the enhanced π-acceptor character of cyaphide over cyanide, while also revealing for the first time an appreciable π-donor component.  The work was highlighted in Chemistry Views Magazine.

 X-ray strucutre of trans-[Ru(dppe)2CN(CP)]

 

[Ru(dppe)2(C≡N)(C≡P)]

Chem. Eur. J., 202127, 16242 - 16246

Alongside our bis(cyaphido) complex we reported this novel trans-cyano-cyaphido complex, the first time cyanide and cyaphide have featured as ligands at the same metal centre.  Computational study of this complex, alongside the cyaphide and carbonyl (see above) allowed an unprecedented insight into the relative donor/acceptor character of this series of ligand analogues.  This work was highlighted in Chemistry Views Magazine.

 The pi-bound benzodiphosphaborolediide complex with molybdenum(0)

 

[Mo(CO)35-(C6H4P2BPh)}{η1-Mo(CO)3(TMEDA)}2].[μ-Li(THF)].[μ-Li(TMEDA)]

Chem. Eur. J., 202127, 16242 - 16246

We recently reported a simple synthetic route to the first example of a diphosphaborolediide - a missing member of the 'hetero-Cp' family of ligands. The aromatic dianion is obtained as its dilithium salt as either a monomeric tmeda solvate, or an oligomeric thf-solvated complex. The ligand also coordinates as a pi-ligand to molybdenum(0), demonstrating its suitability for low- and zero-valent metal centres. This work was highlighted in Chemistry Views Magazine.

 The Benzodiphosphaborolediide dilithium salt as the - oligomeric - thf.

 

[C6H4P2BPh].2[Li(THF)n] A benzodiphosphaborolediide

Chem. Eur. J., 202127, 16242 - 16246

We recently reported a simple synthetic route to the first example of a diphosphaborolediide - a missing member of the 'hetero-Cp' family of ligands. The aromatic dianion is obtained as its dilithium salt as either a monomeric tmeda solvate, or an oligomeric thf-solvated complex. The ligand also coordinates as a pi-ligand to molybdenum(0), demonstrating its suitability for low- and zero-valent metal centres. This work was highlighted in Chemistry Views Magazine.

The Benzodiphosphaborolediide dilithium salt as the tmeda solvate.

 

[C6H4P2BPh].2[Li(TMEDA)] A benzodiphosphaborolediide

Chem. Eur. J., 202127, 16242 - 16246

We recently reported a simple synthetic route to the first example of a diphosphaborolediide - a missing member of the 'hetero-Cp' family of ligands. The aromatic dianion is obtained as its dilithium salt as either a monomeric tmeda solvate, or an oligomeric thf-solvated complex. The ligand also coordinates as a pi-ligand to molybdenum(0), demonstrating its suitability for low- and zero-valent metal centres. This work was highlighted in Chemistry Views Magazine.

 

Archive 2020

The pyridyl-derived diphosphametacyclophane

 

m-{-C(O)-NC5H3-(C(O)PMe)}2

J. Org. Chem., 2020 85, 14697-14707

We recently elaborated our range of diphosphametacyclophanes to include a series of macrocycles featuring substitution in the aromatic 5-position, along with analogues based on pyridyl units and a P-phenyl analogue of our original metacyclophane.  Spectroscopic, cyclic voltammetry and DFT studies probled the photophysical properteis of these molecules, demonstrating their similarity to precedent diketophosphanyl derivatives explored for opto-electronic applications.

The p-Phenyl-diphosphametacyclophane

 

m-{-C(O)-C6H4-(C(O)PPh)}2

J. Org. Chem., 2020 85, 14697-14707

We recently elaborated our range of diphosphametacyclophanes to include a series of macrocycles featuring substitution in the aromatic 5-position, along with analogues based on pyridyl units and a P-phenyl analogue of our original metacyclophane.  Spectroscopic, cyclic voltammetry and DFT studies probled the photophysical properteis of these molecules, demonstrating their similarity to precedent diketophosphanyl derivatives explored for opto-electronic applications.

The 5-(p-cyanophenyl)-substituted P-methyl-diphosphametacyclophane

 

m-{-C(O)-C6H3(p-C6H4CN)-(C(O)PMe)}2

J. Org. Chem., 2020 85, 14697-14707

We recently elaborated our range of diphosphametacyclophanes to include a series of macrocycles featuring substitution in the aromatic 5-position, along with analogues based on pyridyl units and a P-phenyl analogue of our original metacyclophane.  Spectroscopic, cyclic voltammetry and DFT studies probled the photophysical properteis of these molecules, demonstrating their similarity to precedent diketophosphanyl derivatives explored for opto-electronic applications.

The 5-tbutyl-substituted P-methyl-diphosphametacyclophane

 

m-{-C(O)-C6H3tBu-(C(O)PMe)}2

J. Org. Chem., 2020 85, 14697-14707

We recently elaborated our range of diphosphametacyclophanes to include a series of macrocycles featuring substitution in the aromatic 5-position, along with analogues based on pyridyl units and a P-phenyl analogue of our original metacyclophane.  Spectroscopic, cyclic voltammetry and DFT studies probled the photophysical properteis of these molecules, demonstrating their similarity to precedent diketophosphanyl derivatives explored for opto-electronic applications.

The 5-Phenyl-substituted P-methyl-diphosphametacyclophane

 

m-{-C(O)-C6H3Ph-(C(O)PMe)}2

J. Org. Chem., 2020 85, 14697-14707

We recently elaborated our range of diphosphametacyclophanes to include a series of macrocycles featuring substitution in the aromatic 5-position, along with analogues based on pyridyl units and a P-phenyl analogue of our original metacyclophane.  Spectroscopic, cyclic voltammetry and DFT studies probled the photophysical properteis of these molecules, demonstrating their similarity to precedent diketophosphanyl derivatives explored for opto-electronic applications.

The 5-Methyl-substituted P-methyl-diphosphametacyclophane

 

m-{-C(O)-C6H3Me-(C(O)PMe)}2

J. Org. Chem., 2020 85, 14697-14707

We recently elaborated our range of diphosphametacyclophanes to include a series of macrocycles featuring substitution in the aromatic 5-position, along with analogues based on pyridyl units and a P-phenyl analogue of our original metacyclophane.  Spectroscopic, cyclic voltammetry and DFT studies probled the photophysical properteis of these molecules, demonstrating their similarity to precedent diketophosphanyl derivatives explored for opto-electronic applications.

The 5-Iodo-substituted P-methyl-diphosphametacyclophane

 

m-{-C(O)-C6H3I-(C(O)PMe)}2

J. Org. Chem., 2020 85, 14697-14707

We recently elaborated our range of diphosphametacyclophanes to include a series of macrocycles featuring substitution in the aromatic 5-position, along with analogues based on pyridyl units and a P-phenyl analogue of our original metacyclophane.  Spectroscopic, cyclic voltammetry and DFT studies probled the photophysical properteis of these molecules, demonstrating their similarity to precedent diketophosphanyl derivatives explored for opto-electronic applications.

Tungsten pentacarbonyl complex of the P-t-butylphosphinane

 

[W(CO)5(tBu)P{C(O)(CH2)3C(O)}]

Dalton Trans., 2020 49, 5482-5492

We recently reported the first examples of phosphinane-2,6-diones, with a range of P-substituents. These hetercyclic diketyls exhibit a relatively stabilised lone-pair that appears resistant to oxidation and is a somemwhat weaker σ-donor than typical phosphines, which they also lie below in the trans-influence series.  

Tungsten pentacarbonyl complex of the P-Methylphosphinane

 

[W(CO)5(Me)P{C(O)(CH2)3C(O)}]

Dalton Trans., 2020 49, 5482-5492

We recently reported the first examples of phosphinane-2,6-diones, with a range of P-substituents. These hetercyclic diketyls exhibit a relatively stabilised lone-pair that appears resistant to oxidation and is a somemwhat weaker σ-donor than typical phosphines, which they also lie below in the trans-influence series.  

Tungsten pentacarbonyl complex of the P-Phenylphosphinane

 

[W(CO)5(Ph)P{C(O)(CH2)3C(O)}]

Dalton Trans., 2020 49, 5482-5492

We recently reported the first examples of phosphinane-2,6-diones, with a range of P-substituents. These hetercyclic diketyls exhibit a relatively stabilised lone-pair that appears resistant to oxidation and is a somemwhat weaker σ-donor than typical phosphines, which they also lie below in the trans-influence series.  

cis-Pt complex of the P-phenylphosphinane and PEt3

 

cis-[PtCl2(Ph)P{C(O)(CH2)3C(O)}PEt3]

Dalton Trans., 2020 49, 5482-5492

We recently reported the first examples of phosphinane-2,6-diones, with a range of P-substituents. These hetercyclic diketyls exhibit a relatively stabilised lone-pair that appears resistant to oxidation and is a somemwhat weaker σ-donor than typical phosphines, which they also lie below in the trans-influence series.  

The P-Mesityl Phosphinane

 

1-Mesitylphosphinane-2,6-dione

Dalton Trans., 2020 49, 5482-5492

We recently reported the first examples of phosphinane-2,6-diones, with a range of P-substituents. These hetercyclic diketyls exhibit a relatively stabilised lone-pair that appears resistant to oxidation and is a somemwhat weaker σ-donor than typical phosphines, which they also lie below in the trans-influence series.  

The P-phenyl phosphinane

 

1-Phenylphosphinane-2,6-dione

Dalton Trans., 2020 49, 5482-5492

We recently reported the first examples of phosphinane-2,6-diones, with a range of P-substituents. These hetercyclic diketyls exhibit a relatively stabilised lone-pair that appears resistant to oxidation and is a somemwhat weaker σ-donor than typical phosphines, which they also lie below in the trans-influence series.  

Archive 2018-19

5-coordinate Ruthenium-cyaphide cation

 

[Ru(dppe)2(C≡P)]+

Inorg. Chem., 2019 58, 14800-14807

In a particularly exciting step forward for this field, we have now achieved access - by halide abstraction from the trans-halide complexes - to a coordinately unsaturated ruthenium complex of the cyaphide ligand, enabling us to introduce trans-ligands to order (e.g. the carbonyl below).  This circumvents the difficulties associated with installing the cyaphide ligand as a final step, which have previously impeded much work in this area. 

 Trans-carbonyl-cyaphide ruthenium(II) cation

 

[Ru(dppe)2(CO)(C≡P)]+

Inorg. Chem., 2019 58, 14800-14807

 
trans-bromo-cyaphide ruthenium complex

 

[Ru(dppe)2Br(C≡P)]

Inorg. Chem., 2019 58, 14800-14807

The trans-halo complexes [Ru(dppe)2X(CP)] (X = Cl, Br, I) are easily obtained by methide exchange from the parent trans-methyl complex (below) with ZnX2 / PPh3.  This represents the first example of controlled reativity int he coordination sphere of a cyaphide complex - previous such complexes have been found to either be inert, or prone to decomposition with loss of cyaphide.

trans-methyl-cyaphide ruthenium complex

 

[Ru(dppe)2Me(C≡P)]

Inorg. Chem., 2019 58, 14800-14807

The first trans-alkyl-cyaphide complex was prepared using established methods for cyaphide synthesis, commencing from the methyl cation [Ru(dppe)2Me]+, obtained by TlOTf methide metathesis from the dimethyl complex [Ru(dppe)2Me2].  

 


Molecular structure of [Ru(dppe)2(CCCO2Me)(CP)]

 

[Ru(dppe)2(C≡CCO2Me)(C≡P)]

Dalton Trans., 2019 48, 8131-8143

As part of an extended study into the synthesis and electronic nature of complexes featuring the cyaphide ligand through-conjugated (via ruthenium) to a trans-alkynyl we published a range of structures (below), including this structure of one of the first cyaphide complexes we reported (Dalton Trans., 2014 43, 9004 - 9007).

 
Molecular structure of [Ru(dppe)2(CCC6H4F)(CP)]
 

[Ru(dppe)2(C≡CC6H4F)(C≡P)]

Dalton Trans., 2019 48, 8131-8143

 
Molecular structure of [Ru(dppe)2(CCC6H4CO2Me)(CP)]

 

[Ru(dppe)2(C≡CC6H4CO2Me)(C≡P)]

Dalton Trans., 2019 48, 8131-8143

 
Molecular structure of [Ru(dppe)2(CCC6H4F)(PCSiMe3)]+

 

[Ru(dppe)21-P≡CSiMe3)(C≡CC6H4F)]+

Dalton Trans., 2019 48, 8131-8143

As we previously described, each of the cyaphide complexes is prepared by base-induced desilylation of the  η1-bound phosphaalkyne P≡CSiMe3, within the coordination sphere of the respective ruthenium alkynyl complex.

 
Molecular structure of [Ru(dppe)2(CCC6H4Me)(PCSiMe3)]+

 

[Ru(dppe)21-P≡CSiMe3)(C≡CC6H4Me)]+

Dalton Trans., 2019 48, 8131-8143
The HOMO of the through-conjugated bis(ethynyl)benzene bridged biruthenium bis-cyaphide complex

[{Ru(dppe)2}2{μ-(C≡C)2C6H4-p}(C≡P)2]

 

Dalton Trans..2018, 47, 4428 - 4432

We have recently reported the first compound to incorporate two, through-conjugated 'C≡P' moieties; thi unprecedented bimetallic bis-cyaphide complex. 

 

 

Through-conjugated bis(ethynyl)benzene bridged biruthenium bis-eta-1 phosphaalkyne complex

[{Ru(dppe)2}2{μ-(C≡C)2C6H4-p}(η1-P≡CSiMe3)2]

 

Dalton Trans..2018, 47, 4428 - 4432

The first bimetallic complex to feature two η1-phosphaalkyne ligands as part of an extended structure.  This compound serves as precursor in our recent report of the first complex to feature two 'C≡P' ligands as part of a single through-conjugated chain.

 

Archive 2016-17
Molecular structure of [Ru{P(H)ClCH2(SiMe3)}Cl2(CO)(PPh3)2]

[Ru{η1-P(H)Cl–CH2SiMe3)}Cl2(CO)(PPh3)2]

Organometallics.2017, 36, 435 - 442

We recently discovered a remarkably facile cascade reaction, resulting in the double hydrochlorination of our phosphaalkenyl complexes to yield rare examples of the alkylhydrohalophosphane ligand, stabilised in the metal coordination sphere.  The conformational arrangement observed here in the solid state is apparently retained in solution, as evidenced by a Karplus-like coupling dependence for the H-P-Ru-P interactions.
 Molecular structure of  [Ru{eta-1;eta-2-P(pz*)=C(SiMe2C6H4CF3)H}(CO)(PPh3)2]

[Ru{η1-N2-P,C-P(pz*)=CH(SiMe2C6H4CF3)}(CO)(PPh3)2]

Inorganics. 2016, 4, 30

We recently extended our work on chelated pyrazolylphosphaalkene complexes of ruthenium, to consider the structural and spectroscopic features of range os such compounds.  This included only the second crystallographically characetised example.
 molecular structure of tri-orthotolylphosphane oxide

O=P(o-Tol)3

Eur. J. Inorg. Chem. 2016, 4076 - 4082

Archive 2015
 x-ray struture of [Ru{P=C(SiMe2Tol)H}Cl(CO)(PPh3)2]

[Ru{P=C(SiMe2Tol)H}Cl(CO)(PPh3)2]

Organometallics 2015, 34, 2533 - 2542

We recently reported the first structural data for 5-coordinate ruthenaphosphaalkenyl complexes. 
 x-ray struture of [Ru{P=C(SiMe2Ph)H}Cl(CO)(PPh3)2]

[Ru{P=C(SiMe2Ph)H}Cl(CO)(PPh3)2]

Organometallics 2015, 34, 2533 - 2542

We recently reported the first structural data for 5-coordinate ruthenaphosphaalkenyl complexes. 
 x-ray struture of [Ru{P=C(SiMe3)H}Cl(CO)(PPh3)2]

[Ru{P=C(SiMe3)H}Cl(CO)(PPh3)2]

Organometallics 2015, 34, 2533 - 2542

We recently reported the first structural data for 5-coordinate ruthenaphosphaalkenyl complexes. 
Archive 2014
 a Rhodium Chorocarbonyl bis(difuranyl(boraorganyl)phosphane) complex

[Rh(CO)Cl{PFu2(C2H4B(C8H14)}2]

Eur. J. Inorg. Chem. 2014, 5053 - 5062

 Structure of Cp*IrCl2PPh2nPr

[Cp*IrCl2(PPh2nPr)]

Eur. J. Inorg. Chem. 2014, 5053 - 5062

Structure of Ph2BC(Ph)=C(Ph)PPh2 

Ph2BC(Ph)=C(Ph)PPh2

Eur. J. Inorg. Chem. 2014, 5053 - 5062

 Structure of Bu2BC(Bu)=C(Ph)PPh2

Bu2BC(Bu)=C(Ph)PPh2

Eur. J. Inorg. Chem. 2014, 5053 - 5062

molecular structure of a cyaphide-alkynyl complex

[Ru(dppe)2(C≡CC6H4OMe)(C≡P)]

Dalton Trans., 2014 43, 9004 - 9007

We recently described the first examples of cyaphide-alkynyl complexes, which show through-conjugation of the π-systems.

eta-1 phosphalkyne complex of ruthenium(II) methylpropiolate

[Ru(dppe)21-P≡CSiMe3)(C≡CCO2Me)]+

Dalton Trans., 2014 43, 9004 - 9007

An η1-complex of the phosphaalkyne Me3SiC≡P

Molecular struture of chlororuthenium methylpropiolate complex

[Ru(dppe)2(C≡CCO2Me)Cl]

Dalton Trans., 2014 43, 9004 - 9007

Archive 2012-13
A ruthenium eta-2 phosphaalkene complex

[Ru{η1-N2-P,C-P(pz)=CH(SiMe3)}(CO)(PPh3)2]

Organometallics 2013, 32, 2501-2504

We recently described the formation of unprecedented η12-chelating pyrazolylphosphaalkene complexes of ruthenium(0), via nucelophilic attack of pyrazolate at ruthenium(II) phosphaalkenyl complexes.  

A ruthenaphosphaalkenyl

[Ru{η1-P(HgPh)=CH(SiMe3)}Cl2(CO)(PPh3)2]

Organometallics 2013, 32, 2501-2504

An η1-mercuriophosphaalkene complex of ruthenium(II), obtained by reaction of a ruthenium(II) phosphaalkenyl complex with PhHgCl.

The first diphosphametacyclophane

m-{-C(O)-C6H4(C(O)PMe)}2

Chem. Commun. 2012, 48, 5766-5768

We have prepared, via a mild protocol, the first example of a diphosphametacyclophane.  

 

Me3SiCH2P{P(SiMe3)2}2

Dalton Trans. 2012, 41, 278-284

A very reactive polysilyltriphosphane, which behaves as a bidentate chelating ligand.