Phosphaalkene, phospholyl and phosphinine ligands: New tools in coordination chemistry and catalysis

Floch, Pascal Le

doi:10.1016/j.ccr.2005.04.032

Cited by 420 publications

(160 citation statements)

References 251 publications

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“…10 We note that our G3(MP2)-RAD results do not contain scalar relativistic corrections (ranging between -1.5 and -4.0 kJ/mol for the systems under investigations), as compared to reported CCSD(T)/CBS theoretical results. 9,10 Taking into account the sometimes large experimental uncertainties, in particular for PH 2 and HOPO, the present analysis shows that the G3(MP2)-RAD results agree with the available experimental data, a maximal deviation of 7.6 kJ/mol is obtained.…”

Section: Resultssupporting

confidence: 77%

“…The G3(MP2)-RAD, which aims to reproduce reliable estimates of the CCSD(T) energies in sufficiently large basis set, and computationally heavy CCSD(T)/CBS methods yield similar predictions for the heats of formation. Largest deviations exceeding 10 kJ/mol are noticed for PO 2 and HOPO but the predictions are still within the chemical accuracy. Both G3X and G3X2 (based on spin unrestricted calculations) perform equally well.…”

Section: Resultsmentioning

confidence: 81%

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Bond Dissociation Energies of Organophosphorus Compounds: an Assessment of Contemporary Ab Initio Procedures

et al. 2010

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Thermodynamic properties of phosphorus-containing compounds were investigated using high-level ab initio computations. An extended set of contemporary density functional theory (DFT) procedures was assessed for their ability to accurately predict bond dissociation energies of a set of phosphoranyl radicals. The results of meta-and double-hybrids as well as more recent methods, in particular M05, M05-2X, M06 and M06-2X, were compared with benchmark G3(MP2)-RAD values. Standard heats of formation, entropies and heat capacities of a set of ten organophosphorus compounds were determined and the low-cost BMK functional was found to provide results consistent with available experimental data. In addition, bond dissociation enthalpies (BDEs) were computed using the BMK, M05-2X and SCS-ROMP2 procedure. The three methods give the same stability trend. The BDEs of the phosphorus(III) molecules were found to be lower than their phosphorus(V) counterparts. Overall the following ordering is found: BDE(P-OPh) < BDE(P-CH 3 ) < BDE(P-Ph) < BDE(P-OCH 3 ).

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Section: Resultssupporting

confidence: 77%

Section: Resultsmentioning

confidence: 81%

Bond Dissociation Energies of Organophosphorus Compounds: an Assessment of Contemporary Ab Initio Procedures

et al. 2010

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“…Optimal turnovers with MAC were obtained shortly before the substrate was consumed, [54,55] after an induction time of approximately 1 h for both systems. The electron-withdrawing characteristics of the phosphametallocene functionality [56] are consistent with the moderate rates observed (TOF = 83 for Ru, 63 for Fe; compare, for example, 1100 for Phanephos [57] and 5000 h…”

Section: Coordination: Coordination Of Bidentate Phosphanes To Rhosupporting

confidence: 80%

A Comparison of Phosphaferrocene and Phospharuthenocene Ligands in Rh⁺‐Catalysed Enamide Hydrogenation Reactions: Superior Performance of the Phospharuthenocene

Carmichael

Goldet

Klankermayer

et al. 2007

Chemistry A European J

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Enantiopure Cp*-substituted 3,4-dimethyl-5-phenylphosphametallocene-2-methanols (M=Fe, Ru) have been prepared from the corresponding 2-carboxy-(-)-menthylphospholide anion and elaborated into 2-CH(2)PPh(2) phosphametallocenes (13: M=Fe; 14: M=Ru) and 2-CH(2)PtBuR substituted phospharuthenocenes (R=tBu, Me). The crystal structures of complexes [Rh(1,5-cod)(eta(2)-L)](+)BF(4)(-) (L=13, 14) reveal significantly different aryl group configurations. Comparative studies of the hydrogenation of para-substituted N-acetylcinnamate esters with these pre-catalysts show a superior performance for the phospharuthenocene derivative in terms of both rate and enantioselectivity.

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“…[16][17][18] The first semi-analogue of bipyridine with one phosphorus atom, 2-pyridyl-2-phosphinine (NIPHOS), was synthesized by Mathey et al [19,20] Some studies were devoted to the coordination chemistry of this interesting ligand, but it rapidly became obvious that the presence of two electronically different atoms in the same structure made it difficult to handle; [21,22] the phosphorus atom of phosphinines is highly sensitive towards nucleophilic attack, whereas the nitrogen atom of pyridines is easily protonated. [23] A few years ago, we developed several synthetic routes towards 2,2'-biphosphinines (bp), which are exact phosphorus analogues of bipyridines.…”

Section: Introductionmentioning

confidence: 99%

2,2′‐Biphosphinines and 2,2′‐Bipyridines in Homoleptic Dianionic Group 4 Complexes and Neutral 2,2′‐Biphosphinine Group 6 d⁶ Metal Complexes: Octahedral versus Trigonal‐Prismatic Geometries

Lesnard¹,

Cantat²,

Floch³

et al. 2007

Chemistry A European J

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The geometric and electronic structure of formally d(6) tris-biphosphinine [M(bp)(3)](q) and tris-bipyridine [M(bpy)(3)](q) complexes were studied by means of DFT calculations with the B3LYP functional. In agreement with the available experimental data, Group 4 dianionic [M(bp)(3)](2-) complexes (1P-3P for M=Ti, Zr, and Hf, respectively) adopt a trigonal-prismatic (TP) structure, whereas the geometry of their nitrogen analogues [M(bpy)(3)](2-) (1N-3N) is nearly octahedral (OC), although a secondary minimum was found for the TP structures (1N'-3N'). The electronic factors at work in these systems are discussed by means of an MO analysis of the minima, MO correlation diagrams, and thermodynamic cycles connecting the octahedral and trigonal-prismatic limits. In all these complexes, pronounced electron transfer from the metal center to the lowest lying pi* ligand orbitals makes the d(6) electron count purely formal. However, it is shown that the bp and bpy ligands accommodate the release of electron density from the metal in different ways because of a change in the localization of the HOMO, which is a mainly metal-centered orbital in bp complexes and a pure pi* ligand orbital in bpy complexes. The energetic evolution of the HOMO allows a simple rationalization of the progressive change from the TP to the OC structure on successive oxidation of the [Zr(bp)(3)](2-) complex, a trend in agreement with the experimental structure of the monoanionic complex. The geometry of Group 6 neutral complexes [M(bp)(3)] (4P and 5P for M=Mo and W, respectively) is found to be intermediate between the TP and OC limits, as previously shown experimentally for the tungsten complex. The electron transfer from the metal center to the lowest lying pi* ligand orbitals is found to be significantly smaller than for the Group 4 dianionic analogues. The geometrical change between [Zr(bp)(3)](2-) and [W(bp)(3)] is analyzed by means of a thermodynamic cycle and it is shown that a larger ligand-ligand repulsion plays an important role in favoring the distortion of the tungsten complex away from the TP structure.

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Phosphaalkene, phospholyl and phosphinine ligands: New tools in coordination chemistry and catalysis

Cited by 420 publications

References 251 publications

Bond Dissociation Energies of Organophosphorus Compounds: an Assessment of Contemporary Ab Initio Procedures

Bond Dissociation Energies of Organophosphorus Compounds: an Assessment of Contemporary Ab Initio Procedures

A Comparison of Phosphaferrocene and Phospharuthenocene Ligands in Rh⁺‐Catalysed Enamide Hydrogenation Reactions: Superior Performance of the Phospharuthenocene

2,2′‐Biphosphinines and 2,2′‐Bipyridines in Homoleptic Dianionic Group 4 Complexes and Neutral 2,2′‐Biphosphinine Group 6 d⁶ Metal Complexes: Octahedral versus Trigonal‐Prismatic Geometries

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Phosphaalkene, phospholyl and phosphinine ligands: New tools in coordination chemistry and catalysis

Cited by 420 publications

References 251 publications

Bond Dissociation Energies of Organophosphorus Compounds: an Assessment of Contemporary Ab Initio Procedures

Bond Dissociation Energies of Organophosphorus Compounds: an Assessment of Contemporary Ab Initio Procedures

A Comparison of Phosphaferrocene and Phospharuthenocene Ligands in Rh+‐Catalysed Enamide Hydrogenation Reactions: Superior Performance of the Phospharuthenocene

2,2′‐Biphosphinines and 2,2′‐Bipyridines in Homoleptic Dianionic Group 4 Complexes and Neutral 2,2′‐Biphosphinine Group 6 d6 Metal Complexes: Octahedral versus Trigonal‐Prismatic Geometries

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A Comparison of Phosphaferrocene and Phospharuthenocene Ligands in Rh⁺‐Catalysed Enamide Hydrogenation Reactions: Superior Performance of the Phospharuthenocene

2,2′‐Biphosphinines and 2,2′‐Bipyridines in Homoleptic Dianionic Group 4 Complexes and Neutral 2,2′‐Biphosphinine Group 6 d⁶ Metal Complexes: Octahedral versus Trigonal‐Prismatic Geometries