Unusual Metal-Coordinated Zwitterionic P−C−N−C−N−C Phosphido Adducts

Ekubo, Allen T.; Elsegood, Mark R. J.; Lake, Andrew J.; Smith, Martin B.

doi:10.1021/ic1002308

Cited by 6 publications

(2 citation statements)

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“…The platinum atoms in 3 are cis -coordinated, with two μ 2 -phosphanylidene ligands oriented anti with respect to each other, forming a planar four-membered P 2 Pt 2 ring. The P–Pt bond lengths in 3 (2.239(4) and 2.238(3) Å) are very similar to those observed in a related zwitterionic phosphido complex with the P( cyclo -CH 2 N(Bn)CHN(Bn)CH 2 ) ligand (2.2235(10)–2.2316(11) Å, Bn = benzyl) . Despite a slight elongation when compared with 2 , the P–P bond length (2.246(4) Å, WBI 0.84) in 3 is consistent with that of a normal single P–P bond.…”

Section: Resultssupporting

confidence: 75%

“…The P-Pt bond lengths in 3 (2.239(4) and 2.238(3) Å) are very similar to those observed in a related zwitterionic phosphido complex with the P(cyclo-CH2N(Bn)CHN(Bn)CH2) ligand (2.2235(10) -2.2316(11) Å, Bn = benzyl). 11 Despite a slight elongation when compared with 2, the P-P bond length (2.246(4) Å, WBI 0.84) in 3 is consistent with a normal single P-P bond. Mononuclear phosphanylidene-phosphorane complexes of the general formula R'3P→P(R)→(LA) are more common than the dinuclear systems.…”

Section: Resultsmentioning

confidence: 84%

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Reactivity Profile of a Peri-Substitution-Stabilized Phosphanylidene-Phosphorane: Synthetic, Structural, and Computational Studies

et al. 2014

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The reactions of a peri-substitution stabilized phosphanylidene-phosphorane 1 with [AuCl(tht)] or [PtCl2(cod)] afford binuclear complexes [((1)(AuCl)2)2] 2 and [((1)(PtCl2))2] 3, in which four electrons of the ligand are used in bonding to two metal atoms in the bridging arrangement. Reactions of 1 with [Mo(CO)4(nbd)] or (RhCl2Cp*)2 afford mononuclear complexes [(1)2Mo(CO)4] 4 and [(1)RhCl2Cp*] 5, in which two electrons of the ligand are used to form terminal complexes. Formation of these complexes disrupts the negative hyperconjugation at the P-P bond to various extent, which is mirrored by variations in their P-P bond distances (2.179(4)-2.246(4) Å). The P-P bond is ruptured upon formation of the Pd diphosphene complex 6, which is likely to proceed through a phosphinidene intermediate. In air 1 is fully oxidized to phosphonic acid 7. Reactions of 1 with chalcogens under mild conditions generally afford mixtures of products, from which the trithionated 8, dithionated 9, diselenated 10 and monotellurated species 11 were isolated. The bonding in the chalcogeno derivatives is discussed using DFT (B3LYP) and natural bond orbital analysis, which indicates a contribution from a dative bonding in 8-10. The buttressing effect of the peri-backbone is shown to be an essential factor in the formation of the single push-double pull bis(borane) 13. This is demonstrated experimentally through a synthesis parallel to that used to make 13, but lacking the backbone, which leads to different products. The P-P bond distances in the reported products, as well as additional species, are correlated with Wiberg Bond Indices, showing very good agreement for a variety of bonding modes including the negative hyperconjugation.

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Section: Resultssupporting

confidence: 75%

Section: Resultsmentioning

confidence: 84%

Reactivity Profile of a Peri-Substitution-Stabilized Phosphanylidene-Phosphorane: Synthetic, Structural, and Computational Studies

et al. 2014

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Phosphido‐Bridged Di‐ and Trinuclear Palladium Complexes from Electron‐Poor Phosphanes R₂PH (R = C₂F₅, C₆F₅, (CF₃)₂C₆H₃)

et al. 2019

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Electron-withdrawing substituents R in complexes [L n M(PR 2 )] influence the P-M bond length due to a decreased σ-donation and enhanced π-back-bonding, leading to an increased Lewis acidity of the metal ion and therefore strengthening the M-L bond to electron-rich ligands L. This influences the Lewis acidity and the redox behavior of corresponding transition-metal complexes, which is important for the design of optimized catalytic systems. To investigate this effect, the electronpoor phosphanes R 2 PH with R = C 2 F 5 , C 6 F 5 , 2,4-(CF 3 ) 2 C 6 H 3 were treated with Pd(F 6 acac) 2 (F 6 acac = hexafluoroacetylacetonato) [a] 3904 and Pd(acac) 2 (acac = acetylacetonato). While the reaction of the phosphanes with Pd(F 6 acac) 2 in all cases yielded the corresponding phosphido-bridged dinuclear palladium complexes [{(F 6 acac)Pd[μ-(PR 2 )]} 2 ], the compounds obtained in the reaction with Pd(acac) 2 were structurally more diverse. For R = C 2 F 5 , the dinuclear palladium complex [{(acac)Pd{μ-[P(C 2 F 5 ) 2 ]}} 2 ] was obtained, while the reaction with (C 6 F 5 ) 2 PH yielded a trinuclear palladium complex bridged by four phosphido units. All complexes were fully characterized, including X-ray crystallography.complexes with bridging dialkylphosphido units have been reported in the literature, [10] no X-ray structural data are available.The most conducive and feasible procedure to synthesize dinuclear palladium(II) complexes with bridging phosphido units was devised by Shmidt, Belykh and Goremyka. [11] They precisely describe the reaction of Ph 2 PH with Pd(acac) 2 (acac = acetylacetonato) which led to di-and trinuclear palladium complexes bridged by diphenylphosphido units. A related complex featuring chelating F 6 acac ligands (F 6 acac = hexafluoroacetylacetonato), albeit synthesized differently, was published by Röschenthaler et al. including an X-ray structural investigation. [12] Perfluoroalkyl and -aryl groups distinctly influence the electronic properties of phosphane ligands. The HOMO, which correlates with the negative ionization energy, as well as the LUMO, which correlates with the negative electron affinity, of the fluorinated phosphane derivatives are lowered (Figure 1, left), which is expressed in a decreased nucleophilicity of the Eur. 3905Scheme 3. Synthesis of palladium complex 4.Scheme 4. Synthesis of the trinuclear palladium complex 5.Scheme 5. Synthesis of tetrakis[2,4-bis(trifluoromethyl)phenyl]diphosphane, 6.

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Synthesis, metal coordination and structural studies of trisubstituted P{CH2-1-N(H)naphthyl}3 ligands

Carpenter‐Warren

Cunnington

Elsegood

et al. 2017

Inorganica Chimica Acta

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Unusual Metal-Coordinated Zwitterionic P−C−N−C−N−C Phosphido Adducts

Cited by 6 publications

References 30 publications

Reactivity Profile of a Peri-Substitution-Stabilized Phosphanylidene-Phosphorane: Synthetic, Structural, and Computational Studies

Reactivity Profile of a Peri-Substitution-Stabilized Phosphanylidene-Phosphorane: Synthetic, Structural, and Computational Studies

Phosphido‐Bridged Di‐ and Trinuclear Palladium Complexes from Electron‐Poor Phosphanes R₂PH (R = C₂F₅, C₆F₅, (CF₃)₂C₆H₃)

Synthesis, metal coordination and structural studies of trisubstituted P{CH2-1-N(H)naphthyl}3 ligands

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Unusual Metal-Coordinated Zwitterionic P−C−N−C−N−C Phosphido Adducts

Cited by 6 publications

References 30 publications

Reactivity Profile of a Peri-Substitution-Stabilized Phosphanylidene-Phosphorane: Synthetic, Structural, and Computational Studies

Reactivity Profile of a Peri-Substitution-Stabilized Phosphanylidene-Phosphorane: Synthetic, Structural, and Computational Studies

Phosphido‐Bridged Di‐ and Trinuclear Palladium Complexes from Electron‐Poor Phosphanes R2PH (R = C2F5, C6F5, (CF3)2C6H3)

Synthesis, metal coordination and structural studies of trisubstituted P{CH2-1-N(H)naphthyl}3 ligands

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Phosphido‐Bridged Di‐ and Trinuclear Palladium Complexes from Electron‐Poor Phosphanes R₂PH (R = C₂F₅, C₆F₅, (CF₃)₂C₆H₃)