Spirocyclic, macrocyclic and ladder complexes of coinage metals and mercury with dichalcogeno P<sub>2</sub>N<sub>2</sub>-supported anions

Nordheider, Andreas; Hüll, Katharina; Arachchige, Kasun S. Athukorala; Slawin, Alexandra M. Z.; Woollins, J. Derek; Thirumoorthi, Ramalingam; Chivers, Tristram

doi:10.1039/c5dt00159e

Cited by 22 publications

(7 citation statements)

References 40 publications

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“…As in the previous work with L 2– (E = Te), E,E′-chelated complexes were the major products for selenium, but the N,S-chelated isomers predominated for the sulfur systems. The formation of Se,Se′-chelated complexes with p-block elements contrasts with our recent studies of coinage metal complexes in which attempted metathetical reactions of L 2– (E = Se) with silver(I) or gold(I) halides produces macrocycles that incorporate the monoprotonated ligand H L – …”

Section: Discussioncontrasting

confidence: 66%

Main Group Tellurium Heterocycles Anchored by a P₂^VN₂ Scaffold and Their Sulfur/Selenium Analogues

et al. 2015

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A comprehensive investigation of reactions of alkali-metal derivatives of the ditelluro dianion [TeP V (N t Bu)(-N t Bu)]2 2− (L 2− , E = Te) with p-block element halides produced a series of novel heterocycles incorporating P V 2N2 rings, tellurium and group 13-16 elements. The dianion engages in Te,Te′-chelation to the metal center in Ph2Ge and R2Sn (R = t Bu, n Bu, Ph) derivatives; similar behavior was noted for group 14 derivatives of L 2− (E = S, Se). In the case of group 13 trihalides MCl3 (M = Ga, In), neutral spirocyclic complexes (L)M[N t Bu(Te)P V (-N t Bu)2P III N(H) t Bu)] (M = Ga, In) comprised of a Te,Te′-chelated ligand L 2− and a N,Te-bonded ligand resulting from loss of Te and monoprotonation were obtained. In reactions with RPCl2 (R = t Bu, Ad, i Pr2N) a significant difference was observed between Se-and S-containing systems. In the former case, Se,Se′-chelated derivatives were formed in high yields, whereas the N,S-chelated isomers predominated for sulfur. All complexes were characterized by multinuclear (1 H, 31 P, 77 Se, 119 Sn and 125 Te) NMR spectroscopy; this technique was especially 2 useful in the analysis of the mixture of (L)(Se) and (L)(SeSe) obtained from the reaction of Se2Cl2 with L 2− (E = Te). Single crystal X-ray structures were obtained for the spirocyclic In complex (9), (L)GePh2

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Section: Discussioncontrasting

confidence: 66%

Main Group Tellurium Heterocycles Anchored by a P₂^VN₂ Scaffold and Their Sulfur/Selenium Analogues

et al. 2015

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“…10 %) . A recently developed approach involves the incoporation of the well established building block [ t BuN=(E)P(μ‐N t Bu)] 2 2− . Oxidation with elemental iodine yields the (‐E‐E‐) bridged trimeric macrocycle [( t BuN=)P(μ‐N t Bu) 2 (μ‐E 2 )] 3 ( E , Scheme ).…”

Section: Methodsmentioning

confidence: 99%

A Modular Approach to Inorganic Phosphazane Macrocycles

et al. 2017

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Inorganic macrocycles, based on non-carbon backbones, present exciting synthetic challenges in the systematic assembly of inorganic molecules, as well as new avenues in host-guest and supramolecular chemistry. Here we demonstrate a new high-yielding modular approach to a broad range of trimeric and hexameric S- and Se-bridged inorganic macrocycles based on cyclophosphazane frameworks, using the building blocks [S=(H)P(μ-NR)] . The method involves the in situ generation of the key intermediate [E....._ (S....._ )P(μ-NR)] (E=S, Se) dianion, which can be reacted with electrophilic [ClP(μ-NR)] to give P /P hexameric rings or reacted with I to give trimeric P variants. Important issues which are highlighted in this work are the competitive bridging ability of S versus Se in these systems and the synthesis of the first air-stable and chiral inorganic macrocycles.

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“…For example, late transition metal complexes of ansa‐bridged dicyclophosphazanes B (Figure 1), in which chirality can be introduced at the diol bridge and/or at the amido R group, have allowed the observation of match and mismatch effects in enantioselective catalysis, with good enantiomeric excesses being found for the gold‐catalysed hydroamination of γ‐allenyl sulfonamides and the asymmetric nickel‐catalysed three‐component coupling of a diene and an aldehyde [20] . Another key area of interest has been the coordination chemistry of a range of valance‐isoelectronic phosph(III)azane (C, Figure 1) and phosph(V)azane dianions (D and E, Figure 1), particularly in regard to the large number of donor atoms available for metal coordination and the resulting wealth of metal coordination modes observed [7, 21–25] …”

Section: Introductionmentioning

confidence: 99%

“…[20] Anotherk ey area of interest has been the coordinationc hemistry of ar ange of valance-isoelectronicp hosph(III)azane (C, Figure 1) and phosph(V)azane dianions (D and E, Figure 1), particularly in regard to the large number of donora toms available for metal coordination and the resulting wealth of metal coordination modes observed. [7,[21][22][23][24][25] In addition to applicationsa sm etal donor ligands, phosphazane frameworks have recently also formed the basis for a number of H-bonding anion receptor molecules.T hese include simple systems based on dicyclophosph(III)azanes, of the general type [RNHP(m-NR)] 2 ,a nd more elaborate phosphazane macrocycles, like the pentamer [{P(m-N t Bu)} 2 (NH)] 5 . [12,13,26,27] Our recent studies of the modela nion receptor[ (2-py)NHP(m-N t Bu)] 2 (1), showed that the P, N-chelationo ft ransition metals has three important effects, stabilising the P 2 N 2 framework so that it becomes air-and moisture-stable,p re-organising the N-HH -bonding functionality foro ptimum H-bonding to anions, and dramatically increasingt he polarisation of the NÀHb onds ( Figure 2).…”

Section: Introductionmentioning

confidence: 99%

The Coordination Chemistry of the N‐Donor‐Substituted Phosphazanes

Plajer

Bond

Wright

2020

Chemistry A European J

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Phosph(III)azanes, featuring the heterocyclobutane P 2 N 2 ring, have now been established as building blocks in main-group coordination and supramolecular compounds. Previous studies have largely involved their use as neutral Pdonor ligands or as anionic N-donorl igands,d erived from deprotonationo fa mido-phosphazanes [RNHP(m-NR)] 2 .T he use of neutral amido-phosphazanes themselves as chelating, H-bonddonorsi na nion receptors has also been an area of recent interestb ecause of the ease by which the proton acidity and anion binding constantsc an be modulated, by the incorporation of electron-withdrawing exo-a nd endocyclic groups (R) and by the coordination of transition metals to the ring Pa toms. We observed recently that the effecto fP ,N-chelationo fm etal atomst ot he Pa toms of cis-[(2-py)NHP(m-N t Bu)] 2 (2-py = 2-pyridyl) not only pre-organises the NÀHf unctionality foro ptimum H-bondingt oa nions but also resultsi nalarge increase in anion binding constants, well above those for traditional organic receptorsl ike squaramides and ureas. Here, we report ab roader investigation of ligandc hemistry of [(2-py)NHP(m-t NBu)] 2 (and of the new quinolyld erivative[ (8-Qu)NHP(m-N t Bu)] 2 (8-Qu = 8-quinolyl). The additional N-donor functionality of the heterocyclics ubstituentsa nd itsp osition has am arked effect on the anion and metal coordination chemistry of both species, leading to novel structural behaviour and reactivity compared to unfunctionalizedc ounterparts.

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Spirocyclic, macrocyclic and ladder complexes of coinage metals and mercury with dichalcogeno P₂N₂-supported anions

Abstract: Reactions of the dianions [tBuN(E)P(μ-NtBu)]22− (E = Se,S) with M(i) reagents (M = Ag, Au) or HgCl2 produce complexes of [tBu(H)N(E)P(μ-NtBu)2P(E)NtBu]− with spirocyclic, macrocyclic or ladder structures.

Cited by 22 publications

References 40 publications

Main Group Tellurium Heterocycles Anchored by a P₂^VN₂ Scaffold and Their Sulfur/Selenium Analogues

Main Group Tellurium Heterocycles Anchored by a P₂^VN₂ Scaffold and Their Sulfur/Selenium Analogues

A Modular Approach to Inorganic Phosphazane Macrocycles

The Coordination Chemistry of the N‐Donor‐Substituted Phosphazanes

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Spirocyclic, macrocyclic and ladder complexes of coinage metals and mercury with dichalcogeno P2N2-supported anions

Abstract: Reactions of the dianions [tBuN(E)P(μ-NtBu)]22− (E = Se,S) with M(i) reagents (M = Ag, Au) or HgCl2 produce complexes of [tBu(H)N(E)P(μ-NtBu)2P(E)NtBu]− with spirocyclic, macrocyclic or ladder structures.

Cited by 22 publications

References 40 publications

Main Group Tellurium Heterocycles Anchored by a P2VN2 Scaffold and Their Sulfur/Selenium Analogues

Main Group Tellurium Heterocycles Anchored by a P2VN2 Scaffold and Their Sulfur/Selenium Analogues

A Modular Approach to Inorganic Phosphazane Macrocycles

The Coordination Chemistry of the N‐Donor‐Substituted Phosphazanes

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Product

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Spirocyclic, macrocyclic and ladder complexes of coinage metals and mercury with dichalcogeno P₂N₂-supported anions

Main Group Tellurium Heterocycles Anchored by a P₂^VN₂ Scaffold and Their Sulfur/Selenium Analogues

Main Group Tellurium Heterocycles Anchored by a P₂^VN₂ Scaffold and Their Sulfur/Selenium Analogues