NDLI: Transition-Metal Complexes of Tetrylones $[(CO)_{5}W-E(PPh_{3})_{2}]$ and Tetrylenes $[(CO)_{5}W-NHE]$ (E=C–Pb): A Theoretical Study

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Transition-Metal Complexes of Tetrylones $[(CO)_{5}W-E(PPh_{3})_{2}]$ and Tetrylenes $[(CO)_{5}W-NHE]$ (E=C–Pb): A Theoretical Study

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Nguyen, Thi Ai Nhung Frenking, Gernot
Description	Author Affiliation: Nguyen TA ( Fachbereich Chemie, Philipps-Universität Marburg, Germany.)
Abstract	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 WE 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 WE 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 WE 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 WE 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 WE 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 WE bond strength.
ISSN	09476539
e-ISSN	15213765
Journal	Chemistry - A European Journal
Issue Number	40
Volume Number	18
Language	English
Publisher	Wiley-VCH;ChemPubSoc Europe
Publisher Date	2012-10-01
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Catalysis

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