P(CH2CH2PPh2)3 Bridged Group 10 dimetal centres

Wachtler, Helmuth; Schuh, Walter; Ongania, Karl‐Hans; Kopacka, Holger; Wurst, Klaus; Péringer, Paul

doi:10.1039/b201709a

Cited by 6 publications

(2 citation statements)

References 12 publications

(9 reference statements)

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“…The Pd–Pd bond distance of 2.5470 Å indicates a σ-bond between the two Pd(I) centers. The observed Pd–Pd distance is close to the values (2.55 to 2.56 Å) , but is longer than the values (2. 41 to 2.50 Å) reported for the dinuclear Pd(I) complexes containing both chelate and bridging modes of pincer ligands.…”

Section: Resultssupporting

confidence: 75%

Pyrrole-Based New Diphosphines: Pd and Ni Complexes Bearing the PNP Pincer Ligand

et al. 2012

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A new class of diphosphine PNP pincer ligand, 2,5-bis(diphenylphosphinomethyl)pyrrole 2, was synthesized by the reaction between Ph2PH and 2,5-bis(dimethylaminomethyl)pyrrole in 90% yield. The analogous reaction of Ph2PH with 1,9-bis(dimethylaminomethyl)diphenyldipyrrolylmethane readily afforded a PNNP type diphosphine ligand, 1,9-bis(diphenylphosphinomethyl)diphenyldipyrrolylmethane 5 in 92% yield. These phosphine compounds were oxidized with H2O2 and S8 to give the corresponding phosphoryl and thiophosphoryl compounds 6-9 in very good yields. The reaction of the PNP pincer ligand 2 with [PdCl2(PhCN)2] in the presence of Et3N afforded the mononuclear Pd(II) complex, [PdCl{C4H2N-2,5-(CH2PPh2)2-κ(3)PNP}] 10 in 87% yield. Conversely, treatment of 2 with [PdCl2(PhCN)2] in the absence of Et3N gave the dinuclear Pd(II) complex [Pd2Cl4{μ-C4H3N-2,5-(CH2PPh2)2-κ(2)PP}2], the structure which is proposed based on the spectroscopic data. When 2 was treated with Pd(0) precursor [Pd2(dba)3]·CHCl3 the dinuclear Pd(I) complex [Pd2{μ-C4H2N-2,5-(CH2PPh2)2-κ(2)PN,κ(1)P}2], 12, was obtained in 23% yield. The formation of complex 12 is solvent dependent, which transforms into complex 10 in CDCl3 as studied by variable temperature (1)H and (31)P NMR methods. Treatment of 2 with [Ni(OAc)2]·4H2O gave the mononuclear Ni(II) pincer complex [Ni(OAc){C4H2N-2,5-(CH2PPh2)2-κ(3)PNP}], 13, which upon treatment with an excess of LiCl or LiBr or KI afforded the respective halide ion substituted Ni(II) complexes, [NiX{C4H2N-2,5-(CH2PPh2)2-κ(3)PNP}] (X = Cl, Br, and I), 14-16, in very good yields. The structures of 5, 2,5-bis(diphenylphosphorylmethyl)pyrrole 6, 10, 12, and 14-16 were determined by the single crystal X-ray diffraction method. In the structure of 12, two short contacts between the diagonally positioned Pd and P atoms are observed. To understand these weak interactions, density functional theory (DFT) calculations were done and an interaction MO diagram is presented.

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Section: Resultssupporting

confidence: 75%

Pyrrole-Based New Diphosphines: Pd and Ni Complexes Bearing the PNP Pincer Ligand

et al. 2012

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“…Exploring tunable assemblages of heterodinuclear and heteromultinuclear complexes would be thus an important subject and has closely been indebted to designing metal supporting ligands. Among a number of polydentate ligands used to stabilize multimetallic systems, di- and tridentate phosphines, including bis(diphenylphosphino)methane (dppm) and bis[(diphenylphosphino)methyl]phenylphosphine (dpmp), have widely been used to create metal–metal-bonded homo- and heteromultinuclear structures. ,− In general, polyphosphine ligands possess the potential ability to organize heteromultimetallic centers because their variation of denticity may generate uncoordinated dangling phosphorus atoms capable of trapping additional metals; however, polyphosphines containing more than three P atoms have still been limited, owing to their synthetic difficulty and complicated stereoisomerism. − Recently, we have prepared a methylene-bridged linear tetraphosphine ligand, meso -bis[((diphenylphosphino)methyl)phenylphosphino]methane (dpmppm), and demonstrated that it effectively stabilized versatile tetrametallic chains of group 11 metal ions . Two dpmppm ligands assembled four Au I ions in a syn arrangement with respect to the bent Au I 4 string, and the flexible tetragold(I) chain {Au 4 (μ-dpmppm) 2 } 4+ incorporated a counteranion (X) in its bent pocket to afford {[Au 4 (μ-dpmppm) 2 ]X} 3+ (X = PF 6 , Cl) adducts, the structures of which varied depending on the trapped anions and modulated their intriguing luminous properties .…”

Section: Introductionmentioning

confidence: 99%

Heterotrinuclear Complexes with Palladium, Rhodium, and Iridium Ions Assembled by Conformational Switching of a Tetraphosphine Ligand around a Palladium Center

et al. 2011

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Reaction of [PdCl 2 (cod)] with a tetraphosphine, meso-bis[((diphenylphosphino)methyl)phenylphosphino]methane (dpmppm), afforded the mononuclear Pd II complexes [PdCl(dpmppm-κ 3 )]X (X = Cl (1a), PF 6 (1b)); the pincer-type dpmppm ligand coordinates to the Pd atom with two outer and one inner phosphorus atom to form fused six-and four-membered chelate rings. The remaining inner phosphine is uncoordinated and readily reacts with [Cp*MCl 2 ] 2 to give the heterodimetallic complexes [PdCl-(Cp*MCl 2 )(μ-dpmppm-κ 3 ,κ 1 )]X (X = Cl, M = Rh (21a), Ir (21b); X = PF 6 , M = Rh (23a), Ir (23b)). Attachment of the second metal fragment to the uncoordinated phosphine caused a crucial conformational change of the six-membered chelate ring from a stable chair conformation to a twist-boat structure, which concomitantly destabilizes the four-membered ring for its opening reactions. Complexes 21 (X = Cl) were converted to [PdCl 2 (Cp*MCl 2 )(dpmppmO)], in which the terminal P atom is dissociated and oxidized as Ph 2 P(O)CH 2 P(Ph)CH 2 P(Ph)CH 2 PPh 2 (dpmppmO), and in the presence of another 1 equiv of [Cp*M′Cl 2 ] 2 , complexes 21 were readily transformed into the heterotrinuclear complexes [PdCl 2 (Cp*M′Cl 2 )(Cp*MCl 2 )(μdpmppm-κ 2 ,κ 1 ,κ 1 )] (M = M′ = Rh (31a), Ir, (31b); M = Ir, M′ = Rh (31c)), where the third metal M′ is trapped by the terminal P atom with its four-membered-ring opening. Complexes 23 also reacted with another 1 equiv of [Cp*M′Cl 2 ] 2 to afford the heterotrinuclear complexes [PdCl(μ-Cl)(Cp*M′Cl)(Cp*MCl 2 )(μ-dpmppm-κ 2 ,κ 1 ,κ 1 )]PF 6 (M = M′ = Rh (32a), Ir, (32b); M = Ir, M′ = Rh (32c), M = Rh, M′ = Ir (32d)); the additional metal M′ is ligated by the terminal phosphine and is further connected to the Pd atom via a chloride bridge, resulting in a rather electron-deficient M′ center on the basis of cyclic voltammetry. These results exhibited that the addition of a bulky metal fragment to the uncoordinated phosphine of 1 brings about a conformational switch around the Pd center to promote the ring-opening reaction of the four-membered chelate ring, which leads to an incorporation of the third metal fragment to construct heterotrinuclear structures.

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One-pot synthesis of ultra-branched mixed tetradentate tripodal phosphines and phosphine chalcogenides

et al. 2012

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P(CH2CH2PPh2)3 Bridged Group 10 dimetal centres

Cited by 6 publications

References 12 publications

Pyrrole-Based New Diphosphines: Pd and Ni Complexes Bearing the PNP Pincer Ligand

Pyrrole-Based New Diphosphines: Pd and Ni Complexes Bearing the PNP Pincer Ligand

Heterotrinuclear Complexes with Palladium, Rhodium, and Iridium Ions Assembled by Conformational Switching of a Tetraphosphine Ligand around a Palladium Center

One-pot synthesis of ultra-branched mixed tetradentate tripodal phosphines and phosphine chalcogenides

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