Quantum chemistry studies on the Ru–M interactions and the 31P NMR in [Ru(CO)3(Ph2Ppy)2(MCl2)] (M=Zn, Cd, Hg)

Xu, Xuan; Fang, Liang; Chen, Zhao-Xing; Yang, Guochun; Sun, Shuhui; Su, Zhong‐Min

doi:10.1016/j.jorganchem.2006.01.051

Cited by 8 publications

(4 citation statements)

References 44 publications

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“…The LACVP* basis set uses the standard 6-31G* basis set for light elements and the LAC pseudopotential for third-row and heavier elements. It has been shown that the PBE0 functional significantly outperforms the popular B3LYP functional for Ru(II) complexes of general formula [Ru(CO) 3 (Ph 2 Ppy) 2 ] (py = pyridine) . Frequency calculations at 298.15 K were run for all structures at the same level of theory to make sure that a transition state (one imaginary mode) or minimum (zero imaginary modes) is located and to reach zero-point energy (ZPE) correction and thermodynamic properties.…”

Section: Computational Detailsmentioning

confidence: 99%

Ring-Opening of Cyclohexene via Metathesis by Ruthenium Carbene Complexes. A Computational Study

and

Tlenkopatchev

2007

Organometallics

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Cyclohexene (CH) metathesis reaction mediated by the second-generation ruthenium alkylidene catalyst (IMesH2)(PCy3)CI2RuCHPh (1a), ruthenium ester carbene complexes (IMesH2)(PCy3)CI2RuCHCOOMe (1b), and (PCy3)2CI2RuCHCOOMe (1c), where IMesH2 is a 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene group, has been modeled at the PBE0/LACV3P**++//PBE0/LACVP* level of theory. The calculations revealed that the necessary condition for the catalyst to be active in CH ring-opening is the existence of a high-energy π-complex. It has been shown that the complex 4b complies with this condition, while the ruthenium alkylidene 4a does not. The higher reactivity of 1b compared to 1c can be rationalized in terms of better stabilization of the Ru center in transition states by the IMesH2 ligand.

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Section: Computational Detailsmentioning

confidence: 99%

Ring-Opening of Cyclohexene via Metathesis by Ruthenium Carbene Complexes. A Computational Study

and

Tlenkopatchev

2007

Organometallics

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“…They display intense σ*(d)→σ(p) transition spectroscopy , and exhibit potential photocatalysis for hydrogen production. With the exception of Au(I)−Rh(I) complexes, − many heteronuclear complexes with closed-shell electronic configurations have been synthesized, such as Au/Rh/Pt−M′ (M′ belongs to d 6 /d 8 /d 10 /s 2 metal). − …”

Section: Introductionmentioning

confidence: 99%

Theoretical Studies on Metal−Metal Interaction, Excited States, and Spectroscopic Properties of Binuclear Au−Au, Au−Rh, and Rh−Rh Complexes with Diphosphine Ligands: Buildup of Complexity from Monomers to Dimers

et al. 2009

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To understand their photocatalytic activity and application in luminescent materials, a series of gold and rhodium phosphine complexes (mononuclear [Au(I)(PH(3))(2)](+) (1) and [Rh(I)(CNH)(2)(PH(3))(2)](+) (2); homobinuclear [Au(I)(2)(PH(2)CH(2)PH(2))(2)](2+) (3) and [Rh(I)(2)(CNH)(4)(PH(2)CH(2)PH(2))(2)](2+) (4); heterobinuclear [Au(I)Rh(I)(CNH)(2)(PH(2)CH(2)PH(2))(2)](2+) (5), [Au(I)Rh(I)(CNH)(2)(PH(2)NHPH(2))(2)Cl(2)] (6), and [Au(I)Rh(I)(CNH)(2)(PH(2)NHPH(2))(2)](2+) (7); and oxidized derivatives [Au(II)Rh(II)(CNH)(2)(PH(2)CH(2)PH(2))(2)](4+) (8), [Au(II)Rh(II)(CNH)(2)(PH(2)NHPH(2))(2)Cl(3)](+) (9), and [Au(II)Rh(II)(CNH)(2)(PH(2)NHPH(2))(2)](4+) (10)) were investigated using ab initio methods and density functional theory. With the use of the MP2 method, the M-M' distances in 3-7 were estimated to be in the range of 2.76-3.02 A, implying the existence of weak metal-metal interaction. This is further evident in the stretching frequencies and bond orders of M-M'. The two-electron oxidation from 5-7 to their respective partners 8-10 was shown to mainly occur in the gold-rhodium centers. Experimental absorption spectra were well reproduced by our time-dependent density functional theory calculations. The metal-metal interaction results in a large shift of d(z(2)) --> p(z) transition absorptions in binuclear complexes relative to mononuclear analogues and concomitantly produces a low-lying excited state that is responsible for increasing visible-light photocatalytic activities. Upon excitation, the metal-centered transition and the metal-to-metal charge transfer strengthen the metal-metal interaction in triplet excited states for 3-6, while the promotion of electrons into the sigma*(d(z(2))) orbital weakens the interaction in 9.

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“…(It is normal to use the much larger 6-311G** basis set for accurate GIAO simulations on H through Kr, computational resources permitting.) Whereas the accuracy of GIAO calculations with large basis sets tends to be rather good for organic compounds, it is quite clear that in the presence of transition metal ions, δ P predictions with large basis sets are typically only accurate to within 10-25 ppm of the experimental chemical shift [52][53][54] and therefore no better than those employing the 3-21G** basis set reported here.…”

Section: Shielding Tensor Determinationsmentioning

confidence: 72%

Structural, ¹⁰³Rh NMR and DFT Studies of a Bis(phosphane)Rh^III–Porphyrin Derivative

2009

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The synthesis and characterisation of a novel bis(phosphane)-rhodium(III)-porphyrin, [Rh(TPP)(PEtPh 2 ) 2 ]SbF 6 (compound 1; TPP = dianion of 5,10,15,20-tetraphenylporphyrin) is described. The X-ray structure of the bis(dichloromethane) solvate of the complex has a moderately ruffled porphyrin core conformation, which is primarily determined by the relative orientations of the axial phosphane ligands and their steric interaction with the porphyrin phenyl rings. The mean Rh-N and Rh-P bond lengths for 1 are 2.036(5) and 2.401(3) Å, respectively. The mean absolute perpendicular displacements of the porphyrin α-, β-and meso-carbon atoms from the 24-atom porphyrin mean plane measure 0.15(3), 0.11 (8)

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Quantum chemistry studies on the Ru–M interactions and the 31P NMR in [Ru(CO)3(Ph2Ppy)2(MCl2)] (M=Zn, Cd, Hg)

Cited by 8 publications

References 44 publications

Ring-Opening of Cyclohexene via Metathesis by Ruthenium Carbene Complexes. A Computational Study

Ring-Opening of Cyclohexene via Metathesis by Ruthenium Carbene Complexes. A Computational Study

Theoretical Studies on Metal−Metal Interaction, Excited States, and Spectroscopic Properties of Binuclear Au−Au, Au−Rh, and Rh−Rh Complexes with Diphosphine Ligands: Buildup of Complexity from Monomers to Dimers

Structural, ¹⁰³Rh NMR and DFT Studies of a Bis(phosphane)Rh^III–Porphyrin Derivative

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Quantum chemistry studies on the Ru–M interactions and the 31P NMR in [Ru(CO)3(Ph2Ppy)2(MCl2)] (M=Zn, Cd, Hg)

Cited by 8 publications

References 44 publications

Ring-Opening of Cyclohexene via Metathesis by Ruthenium Carbene Complexes. A Computational Study

Ring-Opening of Cyclohexene via Metathesis by Ruthenium Carbene Complexes. A Computational Study

Theoretical Studies on Metal−Metal Interaction, Excited States, and Spectroscopic Properties of Binuclear Au−Au, Au−Rh, and Rh−Rh Complexes with Diphosphine Ligands: Buildup of Complexity from Monomers to Dimers

Structural, 103Rh NMR and DFT Studies of a Bis(phosphane)RhIII–Porphyrin Derivative

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Structural, ¹⁰³Rh NMR and DFT Studies of a Bis(phosphane)Rh^III–Porphyrin Derivative