Synthesis and Structure of the First Heterodinuclear PCP−Pincer−CDP Complex with a Pd−Au d<sup>8</sup>−d<sup>10</sup>Pseudo-Closed-Shell Interaction

Reitsamer, Christian; Schuh, Walter; Kopacka, Holger; Wurst, Klaus; Péringer, Paul

doi:10.1021/om900686r

Cited by 40 publications

(48 citation statements)

References 25 publications

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“…Peringer et al developed P , C , P –CDP pincer complexes of a formal carbone ligand C(dppm) 2 , which was not isolated and characterized, but trapped in the form of its complexes [ 18 , 19 , 20 , 21 , 22 , 23 , 24 ]. The synthetic strategy involved complex redox reactions.…”

Section: Resultsmentioning

confidence: 99%

“…Our synthetic approach was to isolate the free CDP base. Thus, [CH(dppm) 2 ]Cl ( 12 ) [ 18 , 19 ] was treated with an excess of sodium amide (6.5 eq.) in liquid ammonia at −78 °C.…”

Section: Resultsmentioning

confidence: 99%

“…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%

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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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Section: Resultsmentioning

confidence: 99%

“…Our synthetic approach was to isolate the free CDP base. Thus, [CH(dppm) 2 ]Cl ( 12 ) [ 18 , 19 ] was treated with an excess of sodium amide (6.5 eq.) in liquid ammonia at −78 °C.…”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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

et al. 2020

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“…However,t ransitionmetal complexes with such ligandsare currently limited to rhodium, nickel, palladium, platinum,a nd gold. [21][22][23][24][25][26][27][28] Reactivity patterns of complexes 1a Ph -1 d Ph Next, we evaluated whether the unusual reactivity pattern of a reversible BÀHr eductive elimination in the iron(II) complex with the boron-based ligand could be transferred to other donor groups as well. Therefore, the relative stability of the corresponding isomersw as calculated at the B97D/def2-TZVPP level of theory.W ei nvestigated reductivep rotont ransfer from A (Scheme 1), which,i nt he case of X = AlH, BH, and CH, leads to cleavage of the bond to the formed iron(0)a tom in B.F or X = C, proton transfer yields an iron(0) complex with protonated CDP as ac entral donor group (isomer C).…”

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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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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“…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 ortho-directed double lithiation of hexaphenyl-carbodiphosphorane leads to lithium complexes capable to transfer 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(CH2PPh2)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 2pyridyl functionalized N,C,N-carbodiphosphorane CDP(Py)2 (1) were reported [25,26].…”

Section: Introductionmentioning

confidence: 99%

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

Klein

Demirel

Schinabeck

et al. 2020

Preprint

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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 into 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 reaction of 1 with Cu(I) species CuCl, CuI, and CuSPh or via 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 equivalent of an aryl phosphine (PPh3, P(C6H4OMe)3) or one equivalent of a bisphosphine ligands DPEPhos, XantPhos or 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 (PL) were determined to 36% for dicationic [(CuPPh3)2(CDP(Py)2)](PF6)2 (4) and to 60% for neutral [(CuSPh)2(CDP(CH2PPh2)2] (16).

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Synthesis and Structure of the First Heterodinuclear PCP−Pincer−CDP Complex with a Pd−Au d⁸−d¹⁰Pseudo-Closed-Shell Interaction

Cited by 40 publications

References 25 publications

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

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

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

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Synthesis and Structure of the First Heterodinuclear PCP−Pincer−CDP Complex with a Pd−Au d8−d10Pseudo-Closed-Shell Interaction

Cited by 40 publications

References 25 publications

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

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

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

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Synthesis and Structure of the First Heterodinuclear PCP−Pincer−CDP Complex with a Pd−Au d⁸−d¹⁰Pseudo-Closed-Shell Interaction