trans-Difluoro Complexes of Palladium(II)

被引：47

作者：

Grushin, Vladimir V. ^{[1
]}

Marshall, William J. ^{[1
]}

机构：

[1] DuPont Co Inc, Cent Res & Dev, Expt Stn, Wilmington, DE 19880 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2009年 / 131卷 / 03期

关键词：

F REDUCTIVE ELIMINATION; PHOSPHINE; LIGANDS; D(6); CL; PD; FLUOROPYRIDINES; THERMODYNAMICS; AFFINITIES; ACTIVATION;

D O I：

10.1021/ja808975a

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Complexes trans-[(Py)(2)Pd(Ph)(F)] (1; Py = pyridine) and trans-[(t-BuPy)(2)Pd(Ph)(F)] (2; t-BuPy = 4-tert-butylpyridine) have been prepared from the corresponding iodides and AgF. Thermal decomposition of 1 and 2 in anhydrous benzene at 80 degrees C did not result in C-F bond formation, but Pd black and Ph-2 were produced instead, along with novel difluorides trans-[(Py)(2)Pd(F)(2)] (3) and trans-[(t-BuPy)(2)Pd(F)(2)] (4). Both 3 and 4, the first trans-difluoro d(8) square complexes, were independently synthesized from the corresponding diiodides and AgF and fully characterized. Contrary to filled/filled d(n)-p(n) repulsion considerations, the Pd-F bond distances in 3 and 4 are unprecedentedly short, being only 1.947(4)-1.958(4) angstrom and shorter than those in 1 and 2 by 0.12-0.13 angstrom. The mechanism of formation of 3 and 4 and bonding in these complexes are discussed.

引用

页码：918 / +

页数：3

共 36 条

[1] AB-INITIO MOLECULAR-ORBITAL STUDY OF SUBSTITUENT EFFECTS IN VASKA TYPE COMPLEXES (TRANS-IRL(2)(CO)X) - ELECTRON-AFFINITIES, IONIZATION-POTENTIALS, CARBONYL STRETCH FREQUENCIES, AND THE THERMODYNAMICS OF H-2 DISSOCIATIVE ADDITION
ABUHASANAYN, F
GOLDMAN, AS
KROGHJESPERSEN, K
[J]. INORGANIC CHEMISTRY, 1994, 33 (22) : 5122 - 5130
[2] Bridging fluorides and hard/soft mismatch in d6 and d8 complexes:: The case of [Tl(μ-F)3RU(PPh3)3]
Becker, C
Kieltsch, I
Broggini, D
Mezzetti, A
[J]. INORGANIC CHEMISTRY, 2003, 42 (25) : 8417 - 8429
[3] CAULTON KG, 1994, NEW J CHEM, V18, P25
[4] Clark H.C. S., 2000, Advanced Inorganic Fluorides, P51
[5] TRANSITION-METAL FLUORO COMPOUNDS CONTAINING CARBONYL, PHOSPHINE, ARSINE, AND STIBINE LIGANDS
DOHERTY, NM
HOFFMAN, NW
[J]. CHEMICAL REVIEWS, 1991, 91 (04) : 553 - 573
[6] Drago R.S., 1994, Applications of Electrostatic-Covalent Models in Chemistry
[7] The trans influence of F, Cl, Br and I ligands in a series of square-planar Pd(II) complexes.: Relative affinities of halide anions for the metal centre in trans-[(Ph3P)2Pd(Ph)X]
Flemming, JP
Pilon, MC
Borbulevitch, OY
Antipin, MY
Grushin, VV
[J]. INORGANICA CHIMICA ACTA, 1998, 280 (1-2) : 87 - 98
[8] Molecular fluoro palladium complexes
Fraser, SL
Antipin, MY
Khroustalyov, VN
Grushin, VV
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (20) : 4769 - 4770
[9] A series of new fluororhodium(I) complexes
Gil-Rubio, J
Weberndörfer, B
Werner, H
[J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1999, (09): : 1437 - 1444
[10] Fluorination of nonactivated haloarenes via arynes under mild conditions, resulting from further studies toward Ar-F reductive elimination from palladium(H)
Grushin, Vladimir V.
Marshall, William J.
[J]. ORGANOMETALLICS, 2008, 27 (19) : 4825 - 4828

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