Reaction of Double Ylide C(PPh3)2 with [W(CO)6] – Crystal Structures of [(CO)5­W(CCPPh3)] and [(CO)5W{η1‐O2C2(PPh3)2}] and Bonding Analyses of [TM­(CCPR3)] Compounds

Petz, Wolfgang; Neumüller, Bernhard; Tonner, Ralf

doi:10.1002/ejic.200901212

Cited by 16 publications

(12 citation statements)

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“…Different theoretical and experimental studies report the complexation with different transition metal fragments, such as W(CO) 6 , W(CO) 5 , Ni(CO) 4 , Ni(CO) 3 , and AuCl 3b. 22–26 The divalent E 0 analogues, borylene complexes, (BH)L 2 , and N I and P I , labeled nitreones and phospheones, have recently been investigated both theoretically and experimentally 27–30. These compounds exhibit a very similar bent geometry, and reactivity towards Lewis acids and transition metals (AuCl).…”

Section: Introductionmentioning

confidence: 99%

Reactivity of Dicoordinated Stannylones (Sn⁰) versus Stannylenes (Sn^II): An Investigation Using DFT‐Based Reactivity Indices

et al. 2013

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The reactivity of dicoordinated Sn(0) compounds, stannylones, is probed using density functional theory (DFT)-based reactivity indices and compared with the reactivity of dicoordinated Sn(II) compounds, stannylenes. For the former compounds, the influence of different types of electron-donating ligands, such as cyclic and acyclic carbenes, stannylenes and phosphines, on the reactivity of the central Sn atom is analyzed in detail. Sn(0) compounds are found to be relatively soft systems with a high nucleophilicity, and the plots of the Fukui function f(-) for an electrophilic attack consistently predict the highest reactivity on the Sn atom. Next, complexes of dicoordinated Sn compounds with different Lewis acids of variable hardness are computed. In a first part, the double-base character of stannylones is demonstrated in interactions with the hardest Lewis acid H(+). Both the first and second proton affinities (PAs) are high and are well correlated with the atomic charge on the Sn atom, probing its local hardness. These observations are also in line with electrostatic potential plots that demonstrate that the tin atom in Sn(0) compounds bears a higher negative charge in comparison to Sn(II) compounds. Stannylones and stannylenes can be distinguished from each other by the partial charges at Sn and by various reactivity indices. It also becomes clear that there is a smooth transition between the two classes of compounds. We furthermore demonstrate both from DFT-based reactivity indices and from energy decomposition analysis, combined with natural orbitals for chemical valence (EDA-NOCV), that the monocomplexed stannylones are still nucleophilic and as reactive towards a second Lewis acid as towards the first one. The dominating interaction is a strong σ-type interaction from the Sn atom towards the Lewis acid. The interaction energy is higher for complexes with the cation Ag(+) than with the non-charged electrophiles BH(3), BF(3), and AlCl(3).

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Section: Introductionmentioning

confidence: 99%

Reactivity of Dicoordinated Stannylones (Sn⁰) versus Stannylenes (Sn^II): An Investigation Using DFT‐Based Reactivity Indices

et al. 2013

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“…Within the alkynyl component, the shortening of the bond to phosphorus upon passing from 1 a to 4 a[PF 6 ] 2 is pronounced (0.047 ) but the associated CC bond lengthening is small, so the linker largely retains the structural characteristics of an alkyne. Simple [R 3 P + C C] ligands are considered to be strong sdonors and weak p-acceptors, [20] and the relative charge densities obtained here from B3PW91 DFT studies point clearly to dominant valence-bond structure for 4 a 2+ that has Fe II endgroups and a dicationic biphosphane functionality ( Figure 2; NPA charges computed for IVa 2+ : Q Fe À0.14, Q P + 1.45; for Ia: Q Fe À0.13, Q P + 0.96). [21] Cyclic voltammetry experiments performed on isolated 4 a,b[PF 6 ] 2 are consistent with those performed on 1 a,b.…”

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confidence: 99%

Redox‐Induced Reversible PP Bond Formation to Generate an Organometallic σ⁴λ⁴‐1,2‐Biphosphane Dication

et al. 2013

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“…10 Thorough bonding analyses on the isovalent triphosphenium ions and carbodiphosphoranes confirm the presence of "lone pairs" of electrons in frontier orbitals; 11,12 however, the latter have far more precedent to act as a ligand to transition metals and also to main group Lewis acids. [13][14][15][16][17][18][19][20] Of particular note is the ability of B to donate four electrons simultaneously to electron-deficient fragments such as {Ni(CO) 2 } (C), {BH 2 } + (D), {GeCl} + , and {PNR 2 } 2+ (E) that cannot be isolated with one traditional two-electron donor ligand (Fig. 1).…”

Section: Introductionmentioning

confidence: 99%

Utilizing a zwitterionic approach for the synthesis of late transition metal – triphosphenium ion coordination compounds

et al. 2015

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Zwitterionic dicoordinate phosphorus(I) compounds (1 and 2), formally a charge neutral triphosphenium ion or phosphanide, are shown to coordinate to a variety of late transition metals. The reaction of the phosphanide proligands with {Rh(COD)Cl} 2 results in an equilibrium process that varies as a function of temperature or reaction stoichiometry. Palladium(II) compounds have a tendency to chlorinate the borate backbone while giving dimeric coordination compounds (1Pd) and also a decomposition product (3) where the P(I) atom was replaced. Both "lone pairs" of electrons on phosphorus are utilized simultaneously in the dominant product from the reaction of 1 and [PtMe 2 (-SMe 2 )] 2 , while each platinum center ortho-metallated a phenyl substituent on the flanking phosphorus atoms (1Pt). Stable, isolable, and fully characterized dimeric mercury complexes (1Hg and 2Hg) are produced nearly quantitatively from the reaction of the phosphanide proligand with HgCl 2 . All compounds described were structurally characterized using single crystal X-ray diffraction and represent a growing series of zwitterionic P(I) coordination compounds that cannot be isolated when a cationic triphosphenium ion is used. Résumé :Les composés zwitterioniques bis-coordonnés de phosphore(I) (1 et 2), qui sont en fait des ions triphosphénium neutres ou des phosphanures, se sont révélés capables de se coordonner à divers métaux de transition de fin de série. La réaction des proligands phosphanures avec le complexe [Rh(COD)Cl] 2 entraîne un processus d'équilibre qui varie en fonction de la tempéra-ture ou de la stoechiométrie de la réaction. Les composés de palladium(II) ont tendance à chlorer la chaîne principale boratée et à donner, pour leur part, les composés de coordination dimériques (1Pd) ainsi que le produit de décomposition (3) dans lequel l'atome de P(I) a été remplacé. Les deux doublets non liants des électrons du phosphore sont engagés simultanément dans le produit majoritaire provenant de la réaction entre le composé 1 et le complexe [PtMe 2 (-SMe 2 )] 2 . Quant aux noyaux de platine, chacun d'eux s'est inséré en position ortho de l'un des substituants phényles de l'atome de phosphore voisin (1Pt). Des complexes dimériques de mercure (1Hg et 2Hg) stables, isolables et entièrement caractérisés sont produits de façon quasi quantitative par la réaction du proligand phosphanure avec le HgCl 2 . Tous les composés décrits ont été structurellement caractérisés par diffraction des rayons X d'un cristal unique et représentent une série en expansion de composés zwitterioniques de coordination P(I) ne pouvant pas être isolés lorsqu'un cation triphosphénium est utilisé. [Traduit par la Rédaction] Mots-clés : phosphore, zwitterions, chimie de coordination, chimie des éléments du groupe principal.

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Reaction of Double Ylide C(PPh₃)₂ with [W(CO)₆] – Crystal Structures of [(CO)₅W(CCPPh₃)] and [(CO)₅W{η¹‐O₂C₂(PPh₃)₂}] and Bonding Analyses of [TM(CCPR₃)] Compounds

Cited by 16 publications

References 80 publications

Reactivity of Dicoordinated Stannylones (Sn⁰) versus Stannylenes (Sn^II): An Investigation Using DFT‐Based Reactivity Indices

Reactivity of Dicoordinated Stannylones (Sn⁰) versus Stannylenes (Sn^II): An Investigation Using DFT‐Based Reactivity Indices

Redox‐Induced Reversible PP Bond Formation to Generate an Organometallic σ⁴λ⁴‐1,2‐Biphosphane Dication

Utilizing a zwitterionic approach for the synthesis of late transition metal – triphosphenium ion coordination compounds

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Reaction of Double Ylide C(PPh3)2 with [W(CO)6] – Crystal Structures of [(CO)5­W(CCPPh3)] and [(CO)5W{η1‐O2C2(PPh3)2}] and Bonding Analyses of [TM­(CCPR3)] Compounds

Cited by 16 publications

References 80 publications

Reactivity of Dicoordinated Stannylones (Sn0) versus Stannylenes (SnII): An Investigation Using DFT‐Based Reactivity Indices

Reactivity of Dicoordinated Stannylones (Sn0) versus Stannylenes (SnII): An Investigation Using DFT‐Based Reactivity Indices

Redox‐Induced Reversible PP Bond Formation to Generate an Organometallic σ4λ4‐1,2‐Biphosphane Dication

Utilizing a zwitterionic approach for the synthesis of late transition metal – triphosphenium ion coordination compounds

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Reaction of Double Ylide C(PPh₃)₂ with [W(CO)₆] – Crystal Structures of [(CO)₅W(CCPPh₃)] and [(CO)₅W{η¹‐O₂C₂(PPh₃)₂}] and Bonding Analyses of [TM(CCPR₃)] Compounds

Reactivity of Dicoordinated Stannylones (Sn⁰) versus Stannylenes (Sn^II): An Investigation Using DFT‐Based Reactivity Indices

Reactivity of Dicoordinated Stannylones (Sn⁰) versus Stannylenes (Sn^II): An Investigation Using DFT‐Based Reactivity Indices

Redox‐Induced Reversible PP Bond Formation to Generate an Organometallic σ⁴λ⁴‐1,2‐Biphosphane Dication