Why compete when you can share? Competitive reactivity of germanium and phosphorus with selenium

Tam, Eric C. Y.; Harris, Lisa M.; Borren, Elliot; Smith, J. David; Lein, Matthias; Coles, Martyn P.; Fulton, J. Robin

doi:10.1039/c3cc45954c

Cited by 13 publications

(16 citation statements)

References 32 publications

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“…In these cases, phosphorus atom is connected only to one metal center and can exhibit either pyramidal geometry with one lone pair or planar geometry with the lone pair participating in π bonding , . It should be noted that, among the high number of bridged phosphido complexes,, there are many reports of transition metal complexes featuring non‐bridging, terminal phosphido ligands,, including some supported by nacnac ligands . However, only a handful of known terminal phosphido complexes, incorporate iron and, in most cases, these complexes are supported by carbonyl or cyclopentadienyl co‐ligands.…”

Section: Introductionmentioning

confidence: 99%

Syntheses, Structures and Reactivity of Terminal Phosphido Complexes of Iron(II) Supported by a β‐Diketiminato Ligand

et al. 2018

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We report the synthesis of the first series of terminal phosphido iron complexes supported by a -diketiminato ligand (Dippnacnac) and their catalytic activity in dehydrocoupling of secondary phosphines. Anionic and neutral mono-or diphosphido complexes were obtained from the reaction of [(Dippnacnac)FeCl 2 Li(dme) 2 ] with the R 2 PLi (R = iPr, tBu, Cy, Ph) phosphides by tuning the stoichiometric ratio, polarity of the solvent, and the bulkiness of the substituents at the P-atom. The structures of the synthesized compounds were determined by single-crystal X-ray diffraction, which revealed that the iron [a] Reports by Webster et al. [14,27,43,[98][99][100][101][102] on the use of an iron(II) -diketiminato pre-catalyst, [(Dippnacnac)Fe(CH 2 TMS)] for the hydrophosphination of unsaturated hydrocarbons and dehydrocoupling of primary and secondary phosphines postulated the formation of an intermediate terminal phosphido complex. In the case of hydrophosphination, the authors proposed that the active catalyst is a monomeric phosphido complex; however, the active species was isolated as a bridging complex, [(Dippnacnac)Fe(PRH(CH 2 ) 3 CH=CH 2 )] 2 . [27] Worth emphasizing is that this compound is not only the first -diketiminate iron complex bridged by phosphido groups, but also a perfect example highlighting the catalytic potential of lowcoordinate iron compounds. The hydrophosphination and dehydrocoupling processes are both ideally suited for the synthesis of novel P-containing compounds and their catalytic improvements will expand the access to functionalized phosphines, diphosphanes, and other P-containing derivatives.Recently, we have reported a new synthetic method to access iron(II) phosphanylphosphido complexes using as starting materials the -diketiminato complex [(Dippnacnac)FeCl 2 -Li(dme) 2 ] [103] and lithium salts of diphosphanes, R 2 P-P(SiMe 3 )Li (R = iPr, tBu). [104] Due to the propensity of the diphosphorus ligand to undergo P-P bond cleavage, these iron(II) phosphanylphosphido complexes have rather limited catalytic potential. Considering this limitation, we directed our attention to iron(II) complexes with phosphido R 2 P ligands. In this paper, we detail the syntheses, structures, and spectroscopic characterization of the first series of terminal phosphido Fe II complexes stabilized by -diketiminates. We also discuss their thermal stability and catalytic activity in promoting the dehydrocoupling of secondary phosphines. Reaction of [(Dippnacnac)FeCl 2 ] with Ph 2 PLi:To the suspension of [(Dippnacnac)FeCl 2 ] (0.272 g, 0.5 mmol) in 2.5 mL of solvent (tolu-Eur.

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Section: Introductionmentioning

confidence: 99%

Syntheses, Structures and Reactivity of Terminal Phosphido Complexes of Iron(II) Supported by a β‐Diketiminato Ligand

et al. 2018

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“…Group 14/16 nanomaterials have a wide range of applications, from photovoltaic devices to phase change memory materials. − The synthesis of these nanomaterials traditionally involves the treatment of a metal halide source, such as (e.g., GeI 4 , SnCl 2 , or PbCl 2 ) with trioctylphosphine chalcogenide (TOP-E, E = S, Se, Te) in the presence of a surfactant (e.g., oleylamine) to facilitate nanoparticle growth. − Metal phosphanido complexes have been postulated as important intermediates in the nucleation event in nanoparticle growth. , However, the oxidative reactivity of metal phosphanido complexes with chalcogens has received little attention, − especially when a redox-active metal center bears the phosphanido ligand. , When only the phosphanido ligand is capable of undergoing oxidation, two different oxidation products are generally observed, the formation of the phosphinochalcogenoite ligand, [R 2 PE] − , − or the double addition to the phosphinodichalcoganoate ligand, [R 2 PE 2 ] − . ,, Chalcogens have also been shown to oxidize germanium(II) complexes. − With both germanium and phosphorus capable of undergoing oxidation with chalcogens, ,, we were interested in determining the relative preference of chalcogens toward molecules containing a germanium–phosphorus bond.…”

Section: Introductionmentioning

confidence: 99%

The Reactivity of Germanium Phosphanides with Chalcogens

et al. 2017

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The reactivity of germanium phosphanido complexes with elemental chalcogens is reported. Addition of sulfur to [(BDI)GePCy] (BDI = CH{(CH)CN-2,6-iPrCH}) results in oxidation at germanium to form germanium(IV) sulfide [(BDI)Ge(S)PCy] and oxidation at both germanium and phosphorus to form germanium(IV) sulfide dicylohexylphosphinodithioate complex [(BDI)Ge(S)SP(S)Cy], whereas addition of tellurium to [(BDI)GePCy] only gives the chalcogen inserted product, [(BDI)GeTePCy]. This reactivity is different from that observed between [(BDI)GePCy] and selenium. Addition of selenium to the diphenylphosphanido germanium complex, [(BDI)GePPh], results in insertion of selenium into the Ge-P bond to form [(BDI)GeSePCy] as well as the oxidation at phosphorus to give [(BDI)GeSeP(Se)Ph]. In contrast, addition of selenium to the bis(trimethylsilyl)phosphanido germanium complex, [(BDI)GeP(SiMe)], yields the germanium(IV) selenide [(BDI)Ge(Se)P(SiMe)].

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“…The mechanism for nucleation of these particles is poorly understood. Although tertiary phosphines are responsible for chalogen transfer in nanoparticle growth, there is evidence that secondary phosphine (R 2 HPSe and R 2 HPTe) impurities are key in the nucleation step, resulting in the formation of both phosphinochalcogenoite and phosphinodichalcogenoate complexes [LMEPR 2 and LMEP(E)R 2 , respectively; M = Ge, Sn, Pb; E = S, Se, Te; L = anionic ligand such as oleate] as intermediates. , Several examples of group 14 phosphinodichalcogenoate complexes [LMEP(E)PR 2 ] have been reported; − however, outside our studies, , group 14 phosphinochalcogenoite complexes (LMEPR 2 ) have been implicated only through either computational studies or pure speculation; indeed, this type of ligand class has been characterized only on titanium and tungsten centers. , Thus, little is known about the stability and reactivity of such group 14 complexes.…”

Section: Introductionmentioning

confidence: 99%

“…We have recently reported the reactivity of β-diketiminatogermanium phosphanide complexes [(BDI)GePR 2 ] ( 1-Ge-R ; BDI = CH{(CH 3 )CN-2,6- i Pr 2 C 6 H 3 } 2 ; R = Cy, Ph, SiMe 3 ) with chalcogens (E = S, Se, Te) and noted a range of products depending upon both the phosphanido ligand and the chalcogen (Figure ). ,, The lightest chalcogen oxidized both redox-active germanium(II) and phosphorus(III) centers of 1-Ge-Cy to form complexes of the types 3-Ge-Cy-S , 4-Ge-Cy-S 2 , and 5-Ge-Cy-S 3 , whereas the heaviest chalcogen only inserted into the Ge–P bond to form a complex of the type 2-Ge-Cy-Te . Selenium gave products from both insertion and oxidation, e.g., complexes of the type 2-Ge-R-Se (R = Cy, Ph), 3-Ge-R-Se (R = Cy, SiMe 3 ), and 4-Ge-R-Se 2 (R = Cy, Ph).…”

Section: Introductionmentioning

confidence: 99%

Tin and Lead Phosphanido Complexes: Reactivity with Chalcogens

et al. 2017

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The reactivity of tin and lead phosphanido complexes with chalogens is reported. The addition of sulfur to [(BDI)MPCy] (M = Sn, Pb; BDI = CH{(CH)CN-2,6-iPrCH}) results in the formation of phosphinodithioates [(BDI)MSP(S)Cy] regardless of the conditions; however, when selenium is added to [(BDI)MPCy], a selenium insertion product, phosphinoselenoite [(BDI)MSePCy], can be isolated. This compound readily reacts with additional selenium to form the phosphinodiselenoate complex [(BDI)MSeP(Se)Cy]. In contrast, the addition of selenium to [(BDI)SnP(SiMe)] results in the formation of the heavy ether [(BDI)SnSeSiMe]. Differences in the solution and solid-state molecular species of tin phosphinoselenoite and phosphinodiselenoate complexes were probed using multinuclear solution and solid-state NMR spectroscopy.

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Why compete when you can share? Competitive reactivity of germanium and phosphorus with selenium

Abstract: Addition of one equivalent of selenium to a germanium-phosphanide complex results in insertion of selenium into the Ge-P bond, not oxidation at germanium or phosphorus. Addition of excess selenium results in oxidation at phosphorus, although of germanium oxidation is still observed.

Cited by 13 publications

References 32 publications

Syntheses, Structures and Reactivity of Terminal Phosphido Complexes of Iron(II) Supported by a β‐Diketiminato Ligand

Syntheses, Structures and Reactivity of Terminal Phosphido Complexes of Iron(II) Supported by a β‐Diketiminato Ligand

The Reactivity of Germanium Phosphanides with Chalcogens

Tin and Lead Phosphanido Complexes: Reactivity with Chalcogens

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