The ABC in pincer chemistry – From amine- to borylene- and carbon-based pincer-ligands

Maser, Leon; Vondung, Lisa; Langer, Róbert

doi:10.1016/j.poly.2017.09.009

Cited by 67 publications

(45 citation statements)

References 122 publications

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“…However, al arge number of transferred electrons does not necessarily lead to a strong interaction: p-donor interactions in variant III are found to be insignificant (e.g., DE orb,p = 3.3 kcal mol À1 for 2a,s ee the Supporting Information), despite having an on-negligible eigenvalue (n = À0. 19).…”

Section: Eda-nocv Results Of Iron Complexes 2a-dmentioning

confidence: 99%

“…As previously noted, borylenes are not likely to be sufficiently stabilized by tertiaryp hosphines to allow for their isolation, [11] butthese specieshave been reported as ligandscoordinated to at ransition metal. [12,13,18,19] In the case of aluminum(I), the situation is different:a lthought he FeÀAl interaction is rathers trong, the AlH fragment as ac oordinated ligand is not sufficiently stabilized by tertiary phosphine substituents.H owever,w ith carbenes as stabilizing substituents, iron complexes containing ligand-stabilized aluminum(I) as ad onor ligand can be isolated. [20] Moreover,o ur findings show that, for X = BH, CH, and C, the bond in thesec omplexes can be interpreted as ad onor-acceptor bond from the phosphines to the central group, whichi tself acts as an electron-donatingl igand.…”

Section: Eda-nocv Results Of Iron Complexes 2a-dmentioning

confidence: 99%

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Ligands Based on Phosphine‐Stabilized Aluminum(I), Boron(I), and Carbon(0)

Vondung

Jerabek

Langer

2019

Chemistry A European J

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As ystematic quantum chemical study of the bondingi nd 6 -transition-metalc omplexes, containing phosphine-stabilized, main-group-element fragments, (R 3 P) 2 E, as ligands( E = AlH, BH, CH + ,C ), is reported. By using energy decompositiona nalysis, it is demonstrated that as trong MÀ Eb ondi sa ccompanied by weakP ÀEb onds, and vice versa. Although the AlÀMb ond is, for example, found to be very strong,t he weak AlÀPb onds uggestst hat the corresponding metal complexes will not be stable towards phosphine dissociation. The interaction energies for the boron(I)-based ligand are lower,b ut still higher than those for two-carbonbased ligands.F or neutral ligands, electrostatic interactions are the dominating contributions to metal-ligand bonding, whereas for the cationic ligand as ignificant destabilization, with weak orbital and even weaker electrostatic metalligandinteractions, is observed. Finally,for iron(II) complexes, it is demonstrated that different reactivity patterns are expectedf or thef our donor groups:t he experimentally observedr eversible EÀHr eductivee limination of the borylenebased ligand (E = BH) exhibits significantly higherb arriers for the protonated carbodiphosphorane( CDP) ligand (E = CH) and would proceed throughd ifferent intermediates and transition states.F or aluminum, such reaction pathways are not feasible (E = AlH). Moreover, it is demonstrated that the metalh ydrido complexes with CDP ligandsm ight not be stablet owards reduction and isomerization to ap rotonated CDP ligand and areduced metal center.

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Section: Eda-nocv Results Of Iron Complexes 2a-dmentioning

confidence: 99%

Section: Eda-nocv Results Of Iron Complexes 2a-dmentioning

confidence: 99%

Ligands Based on Phosphine‐Stabilized Aluminum(I), Boron(I), and Carbon(0)

Vondung

Jerabek

Langer

2019

Chemistry A European J

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“…A topic of current interest is introducing secondary ligand functions into the CDP frame: Cyclometalation with noble metals rhodium and platinum gave rise to the characterization of C , C , C -pincer ligand complexes with two cyclometalated phenyl rings [ 12 , 13 , 14 , 15 , 16 , 17 ], and an ortho-directed double lithiation of hexaphenyl-carbodiphosphorane leads to lithium complexes that are capable of transfering the C,C,C -pincer ligand synthon [CDP] 2− to any other element of the periodic table [ 17 ]. P , C , P -chelate complexes of a phosphine functionalized CDP ligand CDP(CH 2 PPh 2 ) 2 ( 13 ), formally a carbone C(dppm) 2 (dppm = bis-diphenylphosphinomethane), were characterized, but the free ligand 13 was not isolated so far [ 18 , 19 , 20 , 21 , 22 , 23 , 24 ]. Only recently, complexes of 2-pyridyl functionalized N , C , N -carbodiphosphorane CDP(Py) 2 ( 1 ) have been reported [ 25 , 26 ].…”

Section: Introductionmentioning

confidence: 99%

Cu(I) Complexes of Multidentate N,C,N- and P,C,P-Carbodiphosphorane Ligands and Their Photoluminescence

et al. 2020

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A series of dinuclear copper(I) N,C,N- and P,C,P-carbodiphosphorane (CDP) complexes using multidentate ligands CDP(Py)2 (1) and (CDP(CH2PPh2)2 (13) have been isolated and characterized. Detailed structural information was gained by single-crystal XRD analyses of nine representative examples. The common structural motive is the central double ylidic carbon atom with its characteristic two lone pairs involved in the binding of two geminal L-Cu(I) fragments at Cu–Cu distances in the range 2.55–2.67 Å. In order to enhance conformational rigidity within the characteristic Cu–C–Cu triangle, two types of chelating side arms were symmetrically attached to each phosphorus atom: two 2-pyridyl functions in ligand CDP(Py)2 (1) and its dinuclear copper complexes 2–9 and 11, as well as two diphenylphosphinomethylene functions in ligand CDP(CH2PPh2)2 (13) and its di- and mononuclear complexes 14–18. Neutral complexes were typically obtained via the reaction of 1 with Cu(I) species CuCl, CuI, and CuSPh or via the salt elimination reaction of [(CuCl)2(CDP(Py)2] (2) with sodium carbazolate. Cationic Cu(I) complexes were prepared upon treating 1 with two equivalents of [Cu(NCMe)4]PF6, followed by the addition of either two equivalents of an aryl phosphine (PPh3, P(C6H4OMe)3) or one equivalent of bisphosphine ligands bis[(2-diphenylphosphino)phenyl] ether (DPEPhos), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (XantPhos), or 1,1′-bis(diphenyl-phosphino) ferrocene (dppf). For the first time, carbodiphosphorane CDP(CH2PPh2)2 (13) could be isolated upon treating its precursor [CH(dppm)2]Cl (12) with NaNH2 in liquid NH3. A protonated and a deprotonated derivative of ligand 13 were prepared, and their coordination was compared to neutral CDP ligand 13. NMR analysis and DFT calculations reveal that the most stable tautomer of 13 does not show a CDP (or carbone) structure in its uncoordinated base form. For most of the prepared complexes, photoluminescence upon irradiation with UV light at room temperature was observed. Quantum yields (ΦPL) were determined to be 36% for dicationic [(CuPPh3)2(CDP(Py)2)](PF6)2 (4) and 60% for neutral [(CuSPh)2(CDP(CH2PPh2)2] (16).

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“…[4] One of the promising approaches to stabilize and utilize Group 13 metallylenes as as pectator supporting ligand is to incorporate the Group 13 metal into acomponent of amultidentate ligand. [5] Several pincer-type Group 13 metalloligands and their transition-metal complexes have been developed in which the Group 13 metal coordinates as aZ -type ligand, [6] formally accepting two electrons in avacant p-orbital from the transition metal, or as an X-type ligand, [7] having two anionic ligands on the Group 13 metal and formally donating two electrons to the transition metal. [5] Several pincer-type Group 13 metalloligands and their transition-metal complexes have been developed in which the Group 13 metal coordinates as aZ -type ligand, [6] formally accepting two electrons in avacant p-orbital from the transition metal, or as an X-type ligand, [7] having two anionic ligands on the Group 13 metal and formally donating two electrons to the transition metal.…”

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confidence: 99%

Stabilized Gallylene in a Pincer‐Type Ligand: Synthesis, Structure, and Reactivity of PGa^IP‐Ir Complexes

2019

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The ABC in pincer chemistry – From amine- to borylene- and carbon-based pincer-ligands

Cited by 67 publications

References 122 publications

Ligands Based on Phosphine‐Stabilized Aluminum(I), Boron(I), and Carbon(0)

Ligands Based on Phosphine‐Stabilized Aluminum(I), Boron(I), and Carbon(0)

Cu(I) Complexes of Multidentate N,C,N- and P,C,P-Carbodiphosphorane Ligands and Their Photoluminescence

Stabilized Gallylene in a Pincer‐Type Ligand: Synthesis, Structure, and Reactivity of PGa^IP‐Ir Complexes

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The ABC in pincer chemistry – From amine- to borylene- and carbon-based pincer-ligands

Cited by 67 publications

References 122 publications

Ligands Based on Phosphine‐Stabilized Aluminum(I), Boron(I), and Carbon(0)

Ligands Based on Phosphine‐Stabilized Aluminum(I), Boron(I), and Carbon(0)

Cu(I) Complexes of Multidentate N,C,N- and P,C,P-Carbodiphosphorane Ligands and Their Photoluminescence

Stabilized Gallylene in a Pincer‐Type Ligand: Synthesis, Structure, and Reactivity of PGaIP‐Ir Complexes

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Stabilized Gallylene in a Pincer‐Type Ligand: Synthesis, Structure, and Reactivity of PGa^IP‐Ir Complexes