Syntheses and Crystal Structures of [Hg{C(PPh3)2}2][Hg2I6] and [Cu{C(PPh3)2}2]I and Comparative Theoretical Stud
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- 作者：Wolfgang Petz ; Bernhard Neumu虉ller ; Susanne Klein ; Gernot Frenking
- 刊名：Organometallics
- 出版年：2011
- 出版时间：June 27, 2011
- 年：2011
- 卷：30
- 期：12
- 页码：3330-3339
- 全文大小：972K
- 年卷期：v.30,no.12(June 27, 2011)
- ISSN：1520-6041
文摘
The synthesis and X-ray structure analysis of the carbodiphosphorane (CDP) complexes [Hg{C(PPh3)2}2][Hg2I6] and [Cu{C(PPh3)2}2]I are reported. The cations [Hg{C(PPh3)2}2]2+ and [Cu{C(PPh3)2}2]+ have approximately linearly coordinated metal atoms. Quantum chemical calculations of model compounds bearing N-heterocyclic carbene (NHC) ligands, [M(NHC)2] and [M{C(PH3)2}2] (M = Cu+, Ag+, Au+, Zn2+, Cd2+, Hg2+), have been carried out at the BP86/TZ2P level. The metal鈥搇igand bonds are very strong, and the bond dissociation energies exhibit a V-shaped trend for first-, second-, and third-row transition metals: Ag+ < Cu+ < Au+ and Cd2+ < Zn2+ < Hg2+. The investigation of the bonding situation in the complexes using an energy decomposition analysis shows that the metal鈥搇igand bonding comes mainly from electrostatic attraction. Inspection of the orbital interactions shows that the Mq鈫?NHC)2 and Mq鈫恵C(PH3)2}2 蟽 donation provides between 65 and 75% of the total orbital interactions 螖Eorb. The contribution of the Mq鈫?NHC)2 and Mq鈫抺C(PH3)2}2 蟺 back-donation is very weak. The nature and strength of the donor鈥揳cceptor bonds of the two-electron donor ligand NHC and the four-electron donor ligand CDP with the group 11 and group 12 metal cations are very similar.