Dispersion and Back-Donation Gives Tetracoordinate [Pd(PPh3)4]

被引：70

作者：

Ahlquist, Marten S. G. ^{[1
]}

Norrby, Per-Ola ^{[2
]}

机构：

[1] Royal Inst Technol, Sch Biotechnol, Div Theoret Chem & Biol, S-10691 Stockholm, Sweden

[2] Univ Gothenburg, Dept Chem, SE-41296 Gothenburg, Sweden

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2011年 / 50卷 / 49期

关键词：

18-electron rule; density functional theory; dispersion interactions; ligand dissociation; palladium; EFFECTIVE CORE POTENTIALS; OXIDATIVE ADDITION; PALLADIUM(0) COMPLEXES; ENERGY;

D O I：

10.1002/anie.201105928

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

18e R.I.P. The apparent compliance of [Pd(PPh3)4] ("tetrakis") with the 18-electron rule is not due to an electronic preference on the central metal. Pd is valence-saturated already by two ligands. Further ligand addition gives a minor energy gain, and is only possible due to strong back-bonding. Dispersion corrections are needed for properly describing the interactions between the ligands. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

引用

页码：11794 / 11797

页数：4

共 30 条

[1] On the performance of continuum solvation models for the solvation energy of small anions
Ahlquist, M
Kozuch, S
Shaik, S
Tanner, D
Norrby, PO
[J]. ORGANOMETALLICS, 2006, 25 (01) : 45 - 47
[2] Theoretical evidence for low-ligated palladium(0): [Pd-L] as the active species in oxidative addition reactions
Ahlquist, M
Fristrup, P
Tanner, D
Norrby, PO
[J]. ORGANOMETALLICS, 2006, 25 (08) : 2066 - 2073
[3] Oxidative addition of aryl chlorides to monoligated palladium(0): A DFT-SCRF study
Ahlquist, Marten
Norrby, Per-Ola
[J]. ORGANOMETALLICS, 2007, 26 (03) : 550 - 553
[4] MECHANISM OF OXIDATIVE ADDITION OF PALLADIUM(0) WITH AROMATIC IODIDES IN TOLUENE, MONITORED AT ULTRAMICROELECTRODES
AMATORE, C
PFLUGER, F
[J]. ORGANOMETALLICS, 1990, 9 (08) : 2276 - 2282
[5] MOLECULAR-STRUCTURE OF TETRAKIS(TRIPHENYLPHOSPHINE) PALLADIUM PD[P(C6H5)3]4.0.5C6H6
ANDRIANOV, VG
AKHREM, IS
CHISTOVALOVA, NM
STRUCHKOV, YT
[J]. JOURNAL OF STRUCTURAL CHEMISTRY, 1976, 17 (01) : 111 - 116
[6] [Anonymous], 2009, JAG VERS 7 6
[7] [Anonymous], 2011, ANGEW CHEM-GER EDIT
[8] Binding energy of d10 transition metals to alkenes by wave function theory and density functional theory
Averkiev, Boris B.
Zhao, Yan
Truhlar, Donald G.
[J]. JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 2010, 324 (1-2) : 80 - 88
[9] DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE
BECKE, AD
[J]. JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) : 5648 - 5652
[10] Transition-State Charge Transfer Reveals Electrophilic, Ambiphilic, and Nucleophilic Carbon-Hydrogen Bond Activation
Ess, Daniel H.
Nielsen, Robert J.
Goddard, William A., III
Periana, Roy A.
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (33) : 11686 - +

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