Polynuclear platinum phosphanido/phosphinito complexes: formation of P–O and P–O–P bonds through reductive coupling processes

Ara, Irene; Forniés, Juan; Mastrorilli, Piero; Todisco, Stefano; Gallo, Vito

doi:10.1039/c5dt02593a

Cited by 10 publications

(6 citation statements)

References 66 publications

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“…Finally, the 31 P{ 1 H} NMR spectrum of 1 exhibits a unique resonance, which appears as a broad singlet at δ = −137.0 ppm, and which is assigned to the two equivalent phosphorus atoms of the phosphide ligands, and the broadening of the resonance is probably caused by the coupling of these phosphorus atoms with the ortho fluorine nuclei of the perhalophenyl groups. This highly negative chemical shift closely resembles those observed in the isoelectronic Pt(II)-phosphide systems showing a Pt 2 P 2 four-membered ring [12,13].…”

Section: Synthesis and Spectroscopic Characterizationsupporting

confidence: 77%

Perhalophenyl–Phosphide: A Couple Needed to Stabilize Phosphide–Gold Complexes

Coconubo-Guio,

Rodríguez-Castillo,

Moreno

et al. 2024

Inorganics

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The synthesis of gold(III) and gold(I)–gold(III) complexes with phosphide bridges is still a matter that requires solutions for their marked instability, in spite of the affinity of this metal in both oxidation states for phosphorous donor ligands. In the course of our studies, we realized that the presence of perhalophenyl groups of the type pentafluorophenyl or 3,5-dichlorotrifluorophenyl in the complexes gives rise to an increase in their stability that eases their isolation and structural characterization. In this paper, we describe two new fully characterized neutral compounds of this type to extend the knowledge on this family of compounds, [{Au(C6Cl2F3)2}2(µ-PPh2)2] (1) and [{Au(C6Cl2F3)2(µ-PPh2)2Au}2] (2). In this work, we analyze the role of the perhalophenyl groups in the stability of these complexes by using quantum chemical topology methodologies, specifically employing an analysis of the non-covalent interactions (NCIs) in real space and evaluating the electrostatic potential surfaces (ESP). Our findings reveal the existence of appreciable π-stacking interactions among the perhalophenyl and phenyl groups in both compounds, significantly contributing to the stability of the systems.

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Section: Synthesis and Spectroscopic Characterizationsupporting

confidence: 77%

Perhalophenyl–Phosphide: A Couple Needed to Stabilize Phosphide–Gold Complexes

Coconubo-Guio,

Rodríguez-Castillo,

Moreno

et al. 2024

Inorganics

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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%

“…Although phosphanido groups are classically used to maintain 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 centers. ,,,, This work demonstrates that oxidation of the metal centers in platinum(II) complexes is a way to efficiently trigger an often a priori unpredictable reactivity of bridging phosphanido ligands.…”

Section: Concluding Remarksmentioning

confidence: 99%

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

et al. 2017

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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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“…On the contrary, the 31 P{ 1 H} NMR spectrum of 5'' in THF at 21°C shows a very broad signal at +81 ppm ( 48,49 [RuCl2(Ph2PO2PPh2)(PPh3)({Ph2PO2}2C2H4)], 50 or [Pt3(PPh2POPPh2)(PPh2)(C6F5)2]. 51 These examples were often obtained inadvertently, with the P−O−P fragments resulting from the evolution of R2POH and/or R2(O=)P−PR2 molecules due to isomerisation of P=O bonding in the presence of M 2+ ions (Cu, Co…). [52][53][54] Recently 67 The averages for the P-Cu-P and P-Cu-X angles, respectively 100.6(12) and 117 2 76 the Cu−P bond length is also similar to those measured in 5 and 5'.…”

Section: Formation Of Iron Complexes 3 and 3'mentioning

confidence: 99%

Complexes of the tripodal phosphine ligands PhSi(XPPh₂)₃(X = CH₂, O): synthesis, structure and catalytic activity in the hydroboration of CO₂

et al. 2016

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The coordination chemistry of Fe(2+), Co(2+) and Cu(+) ions was explored with the triphosphine and triphosphinite ligands PhSi{CH2PPh2}3 (1) and PhSi{OPPh2}3 (2), so as to evaluate the impact of the electronic properties of the tripodal phosphorus ligands on the structure and reactivity of the corresponding complexes. The synthesis and characterization of the complexes [Fe(κ(3)-PhSi{CH2PPh2}3)(MeCN)3][OTf]2 (3) (OTf = O3SCF3), [Fe(κ(3)-PhSi{OPPh2}3)(MeCN)3][OTf]2 (3'), [Co(κ(2)-PhSi{CH2PPh2}3)Cl2] (4), [Co(κ(3)-PhSi{OPPh2}3)Cl2] (4'), [Cu(κ(3)-PhSi{CH2PPh2}3)Br] (5) and [Cu(κ(3)-PhSi{OPPh2}3)I] (5') were carried out. The crystal structures of 3, 3', 4, 4', and of the solvates 5·3THF and 5'·THF are reported. Complexes 3-5' were shown to promote the catalytic hydroboration of CO2 with (9-BBN)2 (9-BBN = 9-borabicyclo[3.3.1]nonane). While the iron and cobalt complexes of the triphosphine 1 are more active than the analogous complexes with 2, the opposite trend is observed with the copper catalysts. Overall, the copper catalysts 5 and 5' are both more reactive and more selective than the Fe and Co catalysts, enabling the formation of the acetal H2C(OBBN)2 with a high molar ratio of H2C(OBBN)2 : CH3OBBN up to 92 : 8.

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Polynuclear platinum phosphanido/phosphinito complexes: formation of P–O and P–O–P bonds through reductive coupling processes

Cited by 10 publications

References 66 publications

Perhalophenyl–Phosphide: A Couple Needed to Stabilize Phosphide–Gold Complexes

Perhalophenyl–Phosphide: A Couple Needed to Stabilize Phosphide–Gold Complexes

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

Complexes of the tripodal phosphine ligands PhSi(XPPh₂)₃(X = CH₂, O): synthesis, structure and catalytic activity in the hydroboration of CO₂

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Polynuclear platinum phosphanido/phosphinito complexes: formation of P–O and P–O–P bonds through reductive coupling processes

Cited by 10 publications

References 66 publications

Perhalophenyl–Phosphide: A Couple Needed to Stabilize Phosphide–Gold Complexes

Perhalophenyl–Phosphide: A Couple Needed to Stabilize Phosphide–Gold Complexes

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

Complexes of the tripodal phosphine ligands PhSi(XPPh2)3(X = CH2, O): synthesis, structure and catalytic activity in the hydroboration of CO2

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Complexes of the tripodal phosphine ligands PhSi(XPPh₂)₃(X = CH₂, O): synthesis, structure and catalytic activity in the hydroboration of CO₂