Palladium and Platinum Complexes of a Benzannulated N-Heterocyclic Plumbylene with an Unusual Bonding Mode

Heitmann, Dennis; Pape, Tania; Hepp, Alexander; Mück‐Lichtenfeld, Christian; Grimme, Stefan; Hahn, F. Ekkehardt

doi:10.1021/ja204955f

Cited by 68 publications

(48 citation statements)

References 35 publications

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“…In contrast, the first TM complexes with monodentate NHPb ligands were recently reported by Grimme, Hahn, and co-workers. [60] The geometries of the platinum and palladium complexes (PPh 3 ) 3 TM-NHPb, in which NHPb is a benzoannelated N-heterocyclic plumbylene, show that the NHPb ligand is bonded in a sideon mode, with the plane of the plumbylene almost perpendicular to the metal À Pb bond. This is very similar to the theoretically predicted bonding mode of W-2 Pb.…”

Section: Resultsmentioning

confidence: 99%

“…The authors explained the geometry with an unusual bonding mode in which the metal fragment serves as a donor toward the vacant p orbital of the ligand (PPh 3 ) 3 TM!NHPb. [60] Figure 3 shows also the calculated BDEs for the (CO) 5 W À NHE bonds. There is a continuous decrease from the carbene complex W-2 C (D e = 54.4 kcal mol À1 ) to the lead compound W-2 Pb (D e = 25.5 kcal mol À1 ).…”

Section: Resultsmentioning

confidence: 99%

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Transition‐Metal Complexes of Tetrylones [(CO)₅W‐E(PPh₃)₂] and Tetrylenes [(CO)₅W‐NHE] (E=C–Pb): A Theoretical Study

Nhung

Frenking

2012

Chemistry A European J

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Quantum chemical calculations at the BP86/TZVPP//BP86/SVP level are performed for the tetrylone complexes [W(CO)(5) -E(PPh(3))(2)] (W-1 E) and the tetrylene complexes [W(CO)(5)-NHE] (W-2 E) with E=C-Pb. The bonding is analyzed using charge and energy decomposition methods. The carbone ligand C(PPh(3) ) is bonded head-on to the metal in W-1 C, but the tetrylone ligands E(PPh(3))(2) are bonded side-on in the heavier homologues W-1 Si to W-1 Pb. The W-E bond dissociation energies (BDEs) increase from the lighter to the heavier homologues (W-1 C: D(e) =25.1 kcal mol(-1); W-1 Pb: D(e) =44.6 kcal mol(-1)). The W(CO)(5) ←C(PPh(3))(2) donation in W-1 C comes from the σ lone-pair orbital of C(PPh(3))(2), whereas the W(CO)(5) ←E(PPh(3))(2) donation in the side-on bonded complexes with E=Si-Pb arises from the π lone-pair orbital of E(PPh(3))(2) (the HOMO of the free ligand). The π-HOMO energy level rises continuously for the heavier homologues, and the hybridization has greater p character, making the heavier tetrylones stronger donors than the lighter systems, because tetrylones have two lone-pair orbitals available for donation. Energy decomposition analysis (EDA) in conjunction with natural orbital for chemical valence (NOCV) suggests that the W-E BDE trend in W-1 E comes from the increase in W(CO)(5) ←E(PPh(3))(2) donation and from stronger electrostatic attraction, and that the E(PPh(3))(2) ligands are strong σ-donors and weak π-donors. The NHE ligands in the W-2 E complexes are bonded end-on for E=C, Si, and Ge, but side-on for E=Sn and Pb. The W-E BDE trend is opposite to that of the W-1 E complexes. The NHE ligands are strong σ-donors and weak π-acceptors. The observed trend arises because the hybridization of the donor orbital at atom E in W-2 E has much greater s character than that in W-1 E, and even increases for heavier atoms, because the tetrylenes have only one lone-pair orbital available for donation. In addition, the W-E bonds of the heavier systems W-2 E are strongly polarized toward atom E, so the electrostatic attraction with the tungsten atom is weak. The BDEs calculated for the W-E bonds in W-1 E, W-2 E and the less bulky tetrylone complexes [W(CO)(5) -E(PH(3))(2)] (W-3 E) show that the effect of bulky ligands may obscure the intrinsic W-E bond strength.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Transition‐Metal Complexes of Tetrylones [(CO)₅W‐E(PPh₃)₂] and Tetrylenes [(CO)₅W‐NHE] (E=C–Pb): A Theoretical Study

Nhung

Frenking

2012

Chemistry A European J

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“…( I , Figure 1),7 Grimme et al. ( II , Figure 1),8 and ourselves ( III , Figure 1). 4 A study of the Cambridge Crystallographic Database2 shows that these complexes are the most pyramidalized of all non‐base‐stabilized MER 2 complexes.…”

Section: Introductionmentioning

confidence: 86%

Platinum Complexes Containing Pyramidalized Germanium and Tin Dihalide Ligands Bound through σ,σ ME Multiple Bonds

Hupp

Kroll

et al. 2014

Chemistry A European J

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“…12 That the heavier tetrylenes can display quite different bonding motifs to transition metals has been shown recently by Hahn and co-workers. 13 …”

Section: Introductionmentioning

confidence: 99%

Coordination Chemistry of Cyclic Disilylated Stannylenes and Plumbylenes to Group 4 Metallocenes

et al. 2012

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Reduction of group 4 metallocene dichlorides with magnesium in the presence of cyclic disilylated stannylene or plumbylene phosphine adducts yielded the respective metallocene tetrylene phosphine complexes. Under the same conditions the use of the respective dimerized stannylene or plumbylene gave metallocene ditetrylene complexes. A computational analysis of these reactions revealed for all investigated compounds multiple-bonded character for the M–E(II) linkage, which can be rationalized in the case of the monotetrylene complex with the classical σ-donor/π-acceptor interaction. The strength of the M–E(II) bond increases descending group 4 and decreases going from Sn to its heavier congener Pb. The weakness of the Ti–E(II) bonds is caused by the significantly reduced ability of the titanium atom for d–p π-back-bonding.

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Palladium and Platinum Complexes of a Benzannulated N-Heterocyclic Plumbylene with an Unusual Bonding Mode

Cited by 68 publications

References 35 publications

Transition‐Metal Complexes of Tetrylones [(CO)₅W‐E(PPh₃)₂] and Tetrylenes [(CO)₅W‐NHE] (E=C–Pb): A Theoretical Study

Transition‐Metal Complexes of Tetrylones [(CO)₅W‐E(PPh₃)₂] and Tetrylenes [(CO)₅W‐NHE] (E=C–Pb): A Theoretical Study

Platinum Complexes Containing Pyramidalized Germanium and Tin Dihalide Ligands Bound through σ,σ ME Multiple Bonds

Coordination Chemistry of Cyclic Disilylated Stannylenes and Plumbylenes to Group 4 Metallocenes

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Palladium and Platinum Complexes of a Benzannulated N-Heterocyclic Plumbylene with an Unusual Bonding Mode

Cited by 68 publications

References 35 publications

Transition‐Metal Complexes of Tetrylones [(CO)5W‐E(PPh3)2] and Tetrylenes [(CO)5W‐NHE] (E=C–Pb): A Theoretical Study

Transition‐Metal Complexes of Tetrylones [(CO)5W‐E(PPh3)2] and Tetrylenes [(CO)5W‐NHE] (E=C–Pb): A Theoretical Study

Platinum Complexes Containing Pyramidalized Germanium and Tin Dihalide Ligands Bound through σ,σ ME Multiple Bonds

Coordination Chemistry of Cyclic Disilylated Stannylenes and Plumbylenes to Group 4 Metallocenes

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Transition‐Metal Complexes of Tetrylones [(CO)₅W‐E(PPh₃)₂] and Tetrylenes [(CO)₅W‐NHE] (E=C–Pb): A Theoretical Study

Transition‐Metal Complexes of Tetrylones [(CO)₅W‐E(PPh₃)₂] and Tetrylenes [(CO)₅W‐NHE] (E=C–Pb): A Theoretical Study