Synthesis and Double C-H Activation of Palladium(II) Complexes with the Cationic Ligand [To3PCH2(Py-2)]+ (To = C6H4Me-4, Py = Pyridine). Some Evidence of the Formation of a Palladium(IV) Complex. Crystal and Molecular Structures of trans-[PdCl2{Py{CH2PTo3}-2}2](ClO4)2·4Cl2CH2, [PdCl{μ2-k3-C6H3{PTo2CH(Py-2′)-2}Me-4}]2·2Cl2CH2, and cis-[PdI2{k2-C6H3{PTo2CHCl(Py-2′)-2}Me-4}]·Cl2CH2

José Vicente*, María Teresa Chicote, María Cristina Lagunas, Peter G. Jones, Eberhard Bembenek

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

56 Citations (Scopus)

Abstract

[PdCl2(NCPh)2] reacts with [To3PCH2(Py-2)]ClO4 (1:2) (To = C6H4Me-4, Py = pyridine) or with [To3PCH2(Py-2)]Cl (1:1) to give, respectively, trans-[PdCl2{Py{CH2PTo3}-2}2] (ClO4)2 (1) or [PdCl3{Py{CH2PTo3}-2}] (2). By reacting 1 with 1,8-bis(dimethylamino)naphthalene (1:2 or 1:4) or [To3PCH2(Py-2)]Cl with [PdCl2(NCPh)2] and Na2CO3 (1:1:1), the complex [PdCl{μ2-k3-C6H3{PTo2CH(Py-2′}Me-4}]2·1/2H2O (3) is obtained. This complex reacts (i) with PEt3(1:2) to give (SP-4-3)[PdCl{k2-C6H3{PTo2CH(Py-2′)-2}Me-4}(PEt3)] (4), (ii) with AgClO4 and PEt3 (1:2:2) to give [Pd{k3-C6H3{PTo2CH(Py-2′)-2}Me-4}(PEt3)]2(ClO4)2 (5), (iii) with an excess of Cl2 to give [PdCl2{k2-C6H3{PTo2CHCl(Py-2′)-2}Me-4}] (6), and (iv) with Nal (1:2) to give [PdI{μ2-k3-C6H3{PTo2CH(Py-2′)-2}Me-4}]2 (7). Complex 6 reacts with excess of Nal to give cis-[PdI2{k2-C6H3{PTo2CHCl(Py-2′)-2}Me-4}] (8). The crystal structures of 1·4Cl2CH2, 3·2Cl2-CH2, and 8-Cl2CH2 were determined. [1: space group P1, a = 12.227(4) Å,b = 12.565(4) Å, c = 12.720(4) Å, α= 61.95(2)°, β = 87.44(3)°, γ = 71.89(3)°, V = 1627.2(9) Å3, Z = 1, Rint = 0.024, R(F, >4σ(F)) = 0.036. 3: space group C2/c, a = 23.597(6) Å, b = 8.385(2) Å, c = 27.320(6) Å, β = 99.93(2)°, V = 5325(2) Å3, Z = 4, Rint= 0.029, R(F, >4σ(F)) = 0.028. 7: space group P1, a = 10.379(3) Å, b = 11.961(4) Å, c = 14.289(4) Å, α = 105.03(3)°, β = 97.87(3)°, γ = 113.87(3)°, V = 1506.8(8) Å3, Z = 2, Rint = 0.026, R(F, >4σ(F)) = 0.027.] Complex 1 adopts a trans geometry with short Pd-Cl and Pd-N bond distances [2.2886(11) and 2.035(3) Å, respectively]. The strong trans influence of the Pd-C(methine) and Pd-aryl bonds in complex 3 promotes the lengthening of both the Pd-Cl [2.3725(10) Å] and the Pd-N [2.135(3) Å] bonds. In complex 8 the coordination around the palladium atom is not exactly planar; the N atom lies 0.38 Å out of the plane of the other four atoms.

Original languageEnglish
Pages (from-to)1243-1250
Number of pages8
JournalOrganometallics
Volume13
Issue number4
DOIs
Publication statusPublished - 01 Apr 1994
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Fingerprint

Dive into the research topics of 'Synthesis and Double C-H Activation of Palladium(II) Complexes with the Cationic Ligand [To<sub>3</sub>PCH<sub>2</sub>(Py-2)]<sup>+</sup> (To = C<sub>6</sub>H<sub>4</sub>Me-4, Py = Pyridine). Some Evidence of the Formation of a Palladium(IV) Complex. Crystal and Molecular Structures of trans-[PdCl<sub>2</sub>{Py{CH<sub>2</sub>PTo<sub>3</sub>}-2}<sub>2</sub>](ClO<sub>4</sub>)<sub>2</sub>·4Cl<sub>2</sub>CH<sub>2</sub>, [PdCl{μ<sup>2</sup>-k<sup>3</sup>-C<sub>6</sub>H<sub>3</sub>{PTo<sub>2</sub>CH(Py-2′)-2}Me-4}]2·2Cl<sub>2</sub>CH<sub>2</sub>, and cis-[PdI<sub>2</sub>{k<sup>2</sup>-C<sub>6</sub>H<sub>3</sub>{PTo<sub>2</sub>CHCl(Py-2′)-2}Me-4}]·Cl<sub>2</sub>CH<sub>2</sub>'. Together they form a unique fingerprint.

Cite this