Fragmentation reactions of phosphido and sulphido bridged, trinuclear platinum and palladium clusters and formation of [M2(μ-PPh2)(μ-dppm)(PPh3)2]+, a new type of M(I) cation

Hadj-Bagheri, Nasim; Browning, Jane; Dehghan, Khashayar; Dixon, Keith R.; Meanwell, Neil J.; Vefghi, Rahmatollah

doi:10.1016/0022-328x(90)85484-g

Cited by 19 publications

(9 citation statements)

References 11 publications

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“…The 31 P{ 1 H} NMR spectra of 1a − c recorded at ambient temperature in CD 2 Cl 2 show the pattern of an A 2 X spin system and are flanked by satellites due to coupling with 195 Pt nuclei. The chemical shifts and coupling constants of 1a − c are similar to the values reported for [Pt 2 (μ-dppm)(μ-PPh 2 )(PPh 3 ) 2 ] + . The chemical shift of P1 increases and the value of 1 J (PtP1) decreases in the order PPh 3 ≈ t -BuNC/CO/bicyclo[2.2.1]hept-2-ene.…”

Section: Resultssupporting

confidence: 80%

“…In the [Pt 2 (μ-dppm)(μ-PPh 2 )(bicyclo[2.2.1]hept-2-ene) 2 ] + cation, the Pt1−Pt2 distance (2.7047(6) Å) lies in the range of Pt−Pt bond lengths found for diplatinum(I) complexes and is very similar to the Pd−Pd separation (2.688(2) Å) in the related Pd(I) complex [Pd 2 (μ- i -Pr 2 PCH 2 PPh 2 )(μ-PPh 2 )(PPh 3 ) 2 ] + . The five-membered ring formed by the two Pt atoms and the dppm ligand adopts an envelope conformation with the methylene carbon at the flap.…”

Section: Resultsmentioning

confidence: 65%

“…Extended Hückel calculations showed that the former isomer is slightly more stable. Other examples are the recently reported Pt 3 (μ- t- Bu 2 P) 3 (H)(CO) 2 (44 e, with two short (2.7247(6), 2.7165(6) Å) and one long (3.6135(6) Å) Pt−Pt distances) and the above-mentioned 42-electron clusters [Pt 3 (μ-PPh 2 ) 2 (PPh 3 ) 3 X] + (X = Cl, H, PR 2 , SR) …”

Section: Resultsmentioning

confidence: 94%

“…The [Pt 2 (μ-dppm)(μ-PPh 2 )] framework was previously described in the complex [Pt 2 (μ-dppm)(μ-PPh 2 )(PPh 3 ) 2 ] + , which was obtained by fragmentation of the trinuclear clusters [Pt 3 (μ-PPh 2 ) 2 (PPh 3 ) 3 X] + (X = Cl, H, PR 2 , SR) with dppm …”

Section: Resultsmentioning

confidence: 99%

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Synthesis and Structure of [Pt₃(μ-dppm)₂(μ-PPh₂)L₂](O₃SCF₃) (dppm = Bis(diphenylphosphino)methane; L = CO,t-BuNC)

et al. 1998

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and the methoxyphosphonium salt [PMePh 2 (OMe)](O 3 SCF 3 ). Treatment of 1a with CO (1 atm) or 2 mequiv of t-BuNC gives [Pt 2 (µ-dppm)(µ-PPh 2 )L 2 ](O 3 SCF 3 ) where L ) CO (1b) or t-BuNC (1c). The reaction of 1b or 1c with 1 mequiv of dppm and [Pt(η 2 -bicyclo[2.2.1]hept-2-ene) 3 ], respectively, gives [Pt 3 (µ-dppm) 2 (µ-PPh 2 )L 2 ](O 3 SCF 3 ) where L ) CO (2a) or t-BuNC (2b). The new compounds were characterized by multinuclear NMR, FAB-MS, IR, and chemical analysis, 1a, 2a, and 2b additionally by single-crystal X-ray diffraction. In 1a, the orientation of the CdC double bonds is nearly in plane with the other ligands coordinated to the Pt atoms. The molecular structures of 2a and 2b show Pt 3 triangles whose edges are spanned by two dppm ligands and one PPh 2 ligand. There are bonds between the platinum atoms bridged by the dppm ligands (2.6456(8) and 2.6733(6) Å for 2a and 2.6463(11) and 2.6534(12) Å for 2b) while the separations of the Pt atoms bridged by the PPh 2 ligand are very long (2a, 3.5949(6) Å; 2b, 3.470(1) Å) and are clearly considered as nonbonding. The CO or t-BuNC ligands are coordinated terminally to the Pt atoms bridged by the PPh 2 ligand. The P atom of the phosphido group exhibits a short intramolecular contact to the third Pt atom of 2.954(3) Å (2a) or 2.933(5) Å (2b), which is significantly below the sum of the van der Waals radii of phosphorus and platinum.

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Section: Resultssupporting

confidence: 80%

Section: Resultsmentioning

confidence: 65%

Section: Resultsmentioning

confidence: 94%

Section: Resultsmentioning

confidence: 99%

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Synthesis and Structure of [Pt₃(μ-dppm)₂(μ-PPh₂)L₂](O₃SCF₃) (dppm = Bis(diphenylphosphino)methane; L = CO,t-BuNC)

et al. 1998

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“…The mixed‐bridge Pt I systems [Pt 2 (μ‐PPh 2 )(μ‐dppm)(PPh 3 ) 2 ] + (Pt–Pt) ( 42 )41 and [Pt 2 (μ‐PPh 2 )(μ‐dppm)(norbornene) 2 ] + (Pt–Pt) ( 43 )42 (Scheme ) form: the first by fragmentation of a triangulo Pt 3 cluster, the second by treatment of [Pt 2 (μ‐dppm) 2 Cl 2 ] with norbornene andAgOTf. Complex{(PPh 3 )Pt{μ‐C 6 H 4 (PPh 2 )‐2}}(μ‐PPh 2 )Pt(PPh 3 )] (Pt–Pt) ( 44 ), containing an ortho ‐metallated triphenylphosphane group bridging the Pt I –Pt I bond, is a product of thermolysis of [Pt(PPh 3 ) 2 (C 2 H 4 )]43 and adds electrophilic metal reagents [M(PPh 3 )] + (M = Cu, Ag, Au) at the metal–metal bond 44…”

Section: Phosphanido‐bridged Dinuclear Platinum Complexesmentioning

confidence: 99%

Bridging and Terminal (Phosphanido)platinum Complexes

Mastrorilli¹

2008

Eur J Inorg Chem

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The PR2– group (the phosphanido group, according to the modern IUPAC rules) possesses a strong nucleophilicity, a high bridging tendency and a remarkable flexibility. This review addresses the issue of (phosphanido)platinum complexes, subdividing them into terminal and bridging species. Terminal (phosphanido)platinum complexes are usually prepared by deprotonation of a coordinated secondary (or primary) phosphane on a cationic PtII complex, by an appropriate base. The terminally bonded phosphanide group shows no tendency to form multiple bonds with platinum: in all crystallographically characterised Pt complexes, the terminal phosphanido P atom is pyramidal. Due to the high nucleophilicity granted by the presence of the active lone pair on P, terminal (phosphanido)platinum complexes react with molecules such as O2 and S8, and they can be used for the synthesis of dimetallic compounds upon reaction with suitable metal fragments. The known PtI phosphanido‐bridged complexes are dinuclear, diamagnetic and endowed with a strong Pt–Pt bond. The μ‐PPh2 bridge in PtI dimers arises often by (thermal) activation of the P–C bond in coordinated PPh3 or dppm. PtI phosphanido‐bridged complexes are also prepared by reaction of (dichlorido)platinum complexes with reagents such as Na, NaOH, alcohols. For such complexes a multifaceted reactivity, including the substitution of a terminal ligand, the reaction with electrophiles such as H+ and its isolobal analogues, the insertion into the μ‐P–Pt bond, has been reported. Hydridophosphanido complexes are formed by oxidative addition of a P–H bond onto zero‐valent Pt complexes, by protonation of PtI dimers or by action of BH4– on halido species. Dehydrochlorination of secondary (and primary) phosphane complexes gives chlorido complexes which are mostly prepared in the anti‐[(PRR′2)(Cl)Pt(μ‐PR″2)]2 geometry. Chiral complexes are obtained when asymmetric phosphanido P atoms are present in the molecule. A rich coordination chemistry has been developed on organometallic phosphanido Pt complexes bearing the pentafluorophenyl group. In this framework, a great number of Pt complexes of various nuclearity have been crystallographically characterised and their reactivity towards oxidants studied. The class of polynuclear phosphanido Pt complexes is represented by triangulo species, in which the bridging phosphanide group is typically μ‐PPh2 or μ‐PtBu2, by linear complexes of various nuclearity and by bent species stemming from the presence of a triply bridging diphenylphosphanido ligand in the molecule. Applications of phosphanido Pt complexes in catalysis and materials chemistry are also discussed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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(Phosphido)platinum Complexes by Sodium-Promoted Reaction ofcis-PtCl2(PHCy2)2 − Synthesis and Crystal Structure of [trans-Pt(PCy2H)2(PCy2)Cl], a Rare Example of a Terminal (Phosphido)platinum(II) Complex

Mastrorilli¹,

Nobile²,

Fanizzi³

et al. 2002

Eur. J. Inorg. Chem.

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cis‐PtCl2(PHCy2)2 (1) reacts at 0 °C in toluene with sodium metal to give the dinuclear PtI complexes cis‐[(PHCy2)(H)Pt(μ‐PCy2)]2 (2) and [(PHCy2)(Cl)Pt(μ‐PCy2)Pt(PHCy2)2](Pt−Pt) (3). On standing in solution, complex 3 isomerizes to trans‐[(PHCy2)(Cl)Pt(μ‐PCy2)2Pt(PHCy2)(H)] (4). When treated with sodium at room temperature, complex 3 transforms into [Pt(μ‐PCy2)(PHCy2)]2(Pt−Pt) (5). The sodium reduction of 1 carried out at room temperature leads to the direct formation of the phosphido bridged dinuclear complex [Pt(μ‐PCy2)(PHCy2)]2(Pt−Pt) (5) along with the mononuclear platinum(II) complex [trans‐Pt(PCy2H)2(PCy2)Cl] (6). Complex 6, which has also been obtained by reaction of 1 with LiPCy2, unambiguously shows by single‐crystal X‐ray diffraction the presence of a pyramidal terminal phosphido ligand. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

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Fragmentation reactions of phosphido and sulphido bridged, trinuclear platinum and palladium clusters and formation of [M2(μ-PPh2)(μ-dppm)(PPh3)2]+, a new type of M(I) cation

Cited by 19 publications

References 11 publications

Synthesis and Structure of [Pt₃(μ-dppm)₂(μ-PPh₂)L₂](O₃SCF₃) (dppm = Bis(diphenylphosphino)methane; L = CO,t-BuNC)

Synthesis and Structure of [Pt₃(μ-dppm)₂(μ-PPh₂)L₂](O₃SCF₃) (dppm = Bis(diphenylphosphino)methane; L = CO,t-BuNC)

Bridging and Terminal (Phosphanido)platinum Complexes

(Phosphido)platinum Complexes by Sodium-Promoted Reaction ofcis-PtCl2(PHCy2)2 − Synthesis and Crystal Structure of [trans-Pt(PCy2H)2(PCy2)Cl], a Rare Example of a Terminal (Phosphido)platinum(II) Complex

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Fragmentation reactions of phosphido and sulphido bridged, trinuclear platinum and palladium clusters and formation of [M2(μ-PPh2)(μ-dppm)(PPh3)2]+, a new type of M(I) cation

Cited by 19 publications

References 11 publications

Synthesis and Structure of [Pt3(μ-dppm)2(μ-PPh2)L2](O3SCF3) (dppm = Bis(diphenylphosphino)methane; L = CO,t-BuNC)

Synthesis and Structure of [Pt3(μ-dppm)2(μ-PPh2)L2](O3SCF3) (dppm = Bis(diphenylphosphino)methane; L = CO,t-BuNC)

Bridging and Terminal (Phosphanido)platinum Complexes

(Phosphido)platinum Complexes by Sodium-Promoted Reaction ofcis-PtCl2(PHCy2)2 − Synthesis and Crystal Structure of [trans-Pt(PCy2H)2(PCy2)Cl], a Rare Example of a Terminal (Phosphido)platinum(II) Complex

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Synthesis and Structure of [Pt₃(μ-dppm)₂(μ-PPh₂)L₂](O₃SCF₃) (dppm = Bis(diphenylphosphino)methane; L = CO,t-BuNC)

Synthesis and Structure of [Pt₃(μ-dppm)₂(μ-PPh₂)L₂](O₃SCF₃) (dppm = Bis(diphenylphosphino)methane; L = CO,t-BuNC)