An organometallic tetranuclear cluster with phosphine and phosphido ligands in nonclassical bonding modes: X-ray structural characterization

Chaouche, Naima; Forniés, Juan; Fortuño, Consuelo; Kribii, Abderahim; Martín, António

doi:10.1016/j.jorganchem.2006.11.018

Cited by 21 publications

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References 63 publications

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“…The electron-rich character of the Pt 3 −μ-P 4 bond, i.e., the nucleophilic character of 1, is demonstrated by its reaction with [Pt(C 6 F 5 ) 2 (THF) 2 ], which yields the tetranuclear 4. Formation of the adduct [1·Pt(C 6 F 5 ) 2 ], followed by some ligand rearrangement, [42][43][44]51 can safely explain the isolation of 4.…”

Section: ■ Concluding Remarksmentioning

confidence: 99%

Synthesis and Reactivity of the Unsaturated Trinuclear Phosphanido Complex [(C₆F₅)₂Pt(μ-PPh₂)₂Pt(μ-PPh₂)₂Pt(PPh₃)]

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The reaction of [NBu(4)][(C(6)F(5))(2)Pt(μ-PPh(2))(2)Pt(μ-PPh(2))(2)Pt(O,O-acac)] (48 VEC) with [HPPh(3)][ClO(4)] gives the 46 VEC unsaturated [(C(6)F(5))(2)Pt(1)(μ-PPh(2))(2)Pt(2)(μ-PPh(2))(2)Pt(3)(PPh(3))](Pt(2)-Pt(3)) (1), a trinuclear compound endowed with a Pt-Pt bond. This compound displays amphiphilic behavior and reacts easily with nucleophiles L, yielding the saturated complexes [(C(6)F(5))(2)Pt(II)(μ-PPh(2))(2)Pt(II)(μ-PPh(2))(2)Pt(II)(PPh(3))L] [L = PPh(3) (2), py (3)]. The reaction with the electrophile [Ag(OClO(3))PPh(3)] affords the adduct 1·AgPPh(3), which evolves, even at low temperature, to a mixture in which [(C(6)F(5))(2)Pt(III)(μ-PPh(2))(2)Pt(III)(μ-PPh(2))(2)Pt(II)(PPh(3))(2)](2+)(Pt(III)-Pt(III)) and 2 (plus silver metal) are present. The nucleophilic nature of 1 is also demonstrated through its reaction with cis-[Pt(C(6)F(5))(2)(THF)(2)], which results in the formation of [Pt(4)(μ-PPh(2))(4)(C(6)F(5))(4)(PPh(3))] (4). The structure and NMR features indicate that 1 can be better considered as a Pt(II)-Pt(III)-Pt(I) complex instead of a Pt(II)-Pt(II)-Pt(II) derivative. Theoretical calculations (density functional theory) on similar model compounds are in agreement with the assigned oxidation states of the metal centers. The strong intermetallic interactions resulting in a Pt(2)-Pt(3) metal-metal bond and the respective bonding mechanism were verified by employing a multitude of computational techniques (natural bond order analysis, the Laplacian of the electron density, and localized orbital locator profiles).

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Section: ■ Concluding Remarksmentioning

confidence: 99%

Synthesis and Reactivity of the Unsaturated Trinuclear Phosphanido Complex [(C₆F₅)₂Pt(μ-PPh₂)₂Pt(μ-PPh₂)₂Pt(PPh₃)]

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“…The oxidative addition/reductive elimination process makes the platinum centres to shift between II and IV oxidation states, or III for dinuclear complexes such as in the Although phosphanido groups are classically used for maintaining the molecular architecture of polynuclear transition metal complexes, mainly due to their great flexibility and to the strong P-M bonds, it is now well established that bridging phosphanido groups can act as reaction centres. 51,53,68,71,72…”

Section: Discussionmentioning

confidence: 99%

“…The other platinum(II) centre is bonded to a (pentafluorophenyl)diphenylphosphane group, PPh 2 R F , produced by reductive coupling between a bridging PPh 2 and a pentafluorophenyl group on the Pt(IV) metal centre of the alleged Pt(II),Pt(IV) intermediate. 11,12,14,[50][51][52][53] The anions of 6 and 7 are bimetallic complexes formed by two fragments: "(PPh 2 R F )(R F ) 2 Pt" and "Pt( Figure 9) the signals progressively sharpen and at 198 K the spectrum displays the signals of two interconverting conformers ( 1 H EXSY at 198 K), one of which (labelled A in Figure 9) much more abundant than the other (B). In the 1 H NMR spectrum of the anion of 7 at 198 K were found, beside weak signals attributable to the minor conformer (labelled B in Figure 9), fifteen signals attributable to: the P 2 Ph 2 (ten signals), the pyrimidine rings (three signals), and only two of the ten signals deriving from P(C 6 F 5 )Ph 2 (presumably the para-H of the two phenyl rings) with the remaining eight signals of the P(C 6 F 5 )Ph 2 ligand giving an extremely broad peak ranging from 8.0 to 5.5 ppm (see Figure 9).…”

Section: Reaction Of [(R F )mentioning

confidence: 99%

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Solvent-Driven P–S vs P–C Bond Formation from a Diplatinum(III) Complex and Sulfur-Based Anions

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The outcome of the reaction of the Pt(III),Pt(III) complex [(C 6 F 5) 2 Pt III (µ-PPh 2) 2 Pt III (C 6 F 5) 2 ](Pt-Pt) (1) with the S-based anions thiophenoxide (PhS-), ethyl xanthogenate (EtOCS 2-), 2-mercaptopyrimidinate (pymS-) and 2-mercaptopyridinate (pyS-) was found dependent on the reaction solvent. The reactions carried out in acetone led to the formation of [N n Bu 4 ][(R F) 2 Pt II (μ-PhS-PPh 2)(μ-PPh 2)Pt II (R F) 2 ] (2), [N n Bu 4 ][(R F) 2 Pt II (μ-EtOCS 2-PPh 2)(μ-PPh 2)Pt II (R F) 2 ] (3), [N n Bu 4 ][(R F) 2 Pt II (μ-pymS-PPh 2)(μ-PPh 2)Pt II (R F) 2 ] (4) or [N n Bu 4 ][(R F) 2 Pt II (μ-pyS-PPh 2)(μ-PPh 2)Pt II (R F) 2 ] (5), respectively (R F = C 6 F 5). Complexes 2-5 display new Ph 2 P(SL) ligands exhibiting a κ 2-P,S bridging coordination mode, which derive from a reductive elimination of a PPh 2 group and the S-based anion. Carrying out the reaction in dichloromethane afforded, in the cases of EtOCS 2 and pymSmonobridged complexes [N n Bu 4 ][(PPh 2 R F)(R F) 2 Pt II (μ-PPh 2)Pt II (EtOCS 2)(R F)] (6) and [N n Bu 4 ][(PPh 2 R F)(R F) 2 Pt II (μ-PPh 2)Pt II (pymS)(R F)] (7), respectively, which derive from a reductive elimination of a PPh 2 group with a pentafluorophenyl ring. The reaction of 1 with EtOCS 2 K in acetonitrile yielded a mixture of 3 and 6 as a consequence of the concurrence of two processes: a) the formation of 3 by a reaction that parallels the formation of 3 by 1 plus EtOCS 2 K in acetone; b) the transformation of 1 into the neutral complex [(PPh 2 R F)(CH 3 CN)(R F)Pt II (μ-PPh 2)Pt II (R F) 2 (CH 3 CN)] (8), which, on turn, reacts with EtOCS 2 K to give 6. The 1 to 8 transformation was found to be fully reversible. In fact, dissolving 8 in acetone or dichloromethane afforded pure 1 after solvent evaporation or 2 crystallisation with n-hexane. The XRD structures of 2, 3, 4, 6, 7 and 8 were determined and the behaviour in solution of the new complexes is discussed.

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“…The structures of 1, 3, 4 and 5 are similar. [48][49][50][51][52][53] In each complex, the dihedral angles between Figure 6. The Pt or Pd atoms are at the centres of square-planar coordination environments, which share an edge formed by the P atoms of the two phosphanide bridging ligands.…”

Section: Introductionmentioning

confidence: 99%

Donor Behaviour of Anionic and Asymmetric Phosphanido Derivatives of Platinum and Palladium

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Keywords: Metal-metal interactions / P ligands / Palladium / Platinum / Structure elucidationThe reactions of [Ag(OClO 3 )(PPh 3 )] F 5 )(tht)] (M = Pt, Pd; hq = 8-hydroxyquinolinate, bq = benzoquinolinate, pic = picolinate, tht = tetrahydrothiophene) afford the corresponding neutral adducts [(C 6 F 5 ) 2 Pt-(μ-PPh 2 ) 2 (μ-AgPPh 3 )M(bq)] (M = Pt, 1; Pd, 2), [(C 6 F 5 ) 2 Pt(μ-PPh 2 ) 2 (μ-AgPPh 3 )M(hq)] (M = Pt, 3; Pd, 4) [(C 6 F 5 ) 2 Pt(μ-PPh 2 ) 2 -(μ-AgPPh 3 )Pt(C 6 F 5 )(tht)] (5) and [(C 6 F 5 ) 2 Pt(μ-PPh 2 ) 2 M(pic-AgPPh 3 )] (M = Pt, 6; Pd, 7) as yellow solids. The XRD structures of 1-5, in which a [AgPPh 3 ] + moiety bridges the metal Eur. 1679centres, were confirmed in solution at low temperature. At room temperature, a dynamic process for the [AgPPh 3 ] + moiety, which passes from the top to the bottom part of the molecules 1-5, was ascertained. For 6 and 7, the XRD analyses revealed structures in which the [AgPPh 3 ] + moiety is linked to the picolinate oxygen atom bonded to the M centre; however, although such a structure was confirmed in solution for the Pt-Pd species 7, the stable form of the Pt-Pt species 6 in solution is that with the [AgPPh 3 ] + moiety bridging the metal centres.www.eurjic.org FULL PAPER Scheme 1. num(III) (Scheme 1, type F) and the consequent formation of metallic silver. [38,[42][43][44] Finally, an example has been reported in which the L-LЈ ligand of [Ag 2 {Pt 2 (μ-PPh 2 ) 2 -(C 6 F 5 ) 2 (acac)} 2 ] (acac = acetylacetonate) acts as donor towards the silver atom (Scheme 1, type G and H). [36] In our experience, the results obtained so far in these types of reactions indicate that it is impossible to predict the behaviour of a particular complex towards Ag I .Recently, we have reported the reactions of I 2 with [NBu 4 ][(C 6 F 5 ) 2 Pt II (μ-PPh 2 ) 2 M II (C ∧ N)] [45] and [NBu 4 ]-[(C 6 F 5 ) 2 Pt II (μ-PPh 2 ) 2 M II (O ∧ N)] [46] [M = Pt, Pd; C ∧ N = benzoquinolinate (bq); O ∧ N = 8-hydroxyquinolinate (hq), picolinate (pic)], which contain dinuclear asymmetric anionic complexes and a chelate ligand. In all cases, the addition of molecular I 2 to the complexes resulted in oxidation of the metal centre and the formation of M II -M IV intermediates, which evolved through a PPh 2 /C ∧ N or PPh 2 / O ∧ N reductive coupling with the formation of new M II -M II compounds.In this paper, we report the results obtained in the reactions of anionic complexes of platinum(II) and palladium(II) containing benzoquinolinate, 8-hydroxyquinolinate, tetrahydrothiophene (tht) and picolinate ligands with [AgPPh 3 (OClO 3 )]; these reactions were performed to establish the type of complex (A-H, Scheme 1) obtained when the different dinuclear phosphanido platinum or palladium fragments are reacted with Ag I salts. Results Synthesis and Solid-State StructuresThe addition of [Ag(OClO 3 )(PPh 3 )] to CH 2 Cl 2 solutions of [NBu 4 ][(C 6 F 5 ) 2 Pt(μ-PPh 2 ) 2 M(hq)], [46] [NBu 4 ][(C 6 F 5 ) 2 -Eur.

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An organometallic tetranuclear cluster with phosphine and phosphido ligands in nonclassical bonding modes: X-ray structural characterization

Cited by 21 publications

References 63 publications

Synthesis and Reactivity of the Unsaturated Trinuclear Phosphanido Complex [(C₆F₅)₂Pt(μ-PPh₂)₂Pt(μ-PPh₂)₂Pt(PPh₃)]

Synthesis and Reactivity of the Unsaturated Trinuclear Phosphanido Complex [(C₆F₅)₂Pt(μ-PPh₂)₂Pt(μ-PPh₂)₂Pt(PPh₃)]

Solvent-Driven P–S vs P–C Bond Formation from a Diplatinum(III) Complex and Sulfur-Based Anions

Donor Behaviour of Anionic and Asymmetric Phosphanido Derivatives of Platinum and Palladium

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An organometallic tetranuclear cluster with phosphine and phosphido ligands in nonclassical bonding modes: X-ray structural characterization

Cited by 21 publications

References 63 publications

Synthesis and Reactivity of the Unsaturated Trinuclear Phosphanido Complex [(C6F5)2Pt(μ-PPh2)2Pt(μ-PPh2)2Pt(PPh3)]

Synthesis and Reactivity of the Unsaturated Trinuclear Phosphanido Complex [(C6F5)2Pt(μ-PPh2)2Pt(μ-PPh2)2Pt(PPh3)]

Solvent-Driven P–S vs P–C Bond Formation from a Diplatinum(III) Complex and Sulfur-Based Anions

Donor Behaviour of Anionic and Asymmetric Phosphanido Derivatives of Platinum and Palladium

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Synthesis and Reactivity of the Unsaturated Trinuclear Phosphanido Complex [(C₆F₅)₂Pt(μ-PPh₂)₂Pt(μ-PPh₂)₂Pt(PPh₃)]

Synthesis and Reactivity of the Unsaturated Trinuclear Phosphanido Complex [(C₆F₅)₂Pt(μ-PPh₂)₂Pt(μ-PPh₂)₂Pt(PPh₃)]