Reactivity of 2-(Diphenylphosphanyl)thiophenol (HSC6H4PPh2) with Ruthenium and Osmium Carbonyl Complexes; Breaking of HSC6H4PPh2 into Sulfide, Phenyl and Diphenylphosphanyl Ligands on a Triruthenium Cluster

Cabeza, Javier A.; Martínez-García, M. Angeles; Ardura, Diego; Garcı́a-Granda, Santiago

doi:10.1002/(sici)1099-0682(199903)2000:3<499::aid-ejic499>3.0.co;2-j

Cited by 20 publications

(7 citation statements)

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“…The pendant PPh 3 phosphonium group adds oxidatively to the Pt(II) metal center in B to give the phenylphosphino Pt(IV) derivative C , which is basically identical with the isolated complex 6 . While the P−C bond activation process in phosphine groups promoted by transition metals is a known process, the related P−C bond activation where the PPh n R 3 - n unity belongs to a phosphonium or an ylide functionality is rare . In fact, this type of P−C bond activation on ylide or phosphonium salts have been described to proceed usually with metals in low oxidation states and results in interesting reactions: synthesis of catalysts for the polymerization of ethylene, 31a,b studies and applications of aryl−aryl exchange processes, 31d-m and synthesis of iminophosphoranes. 31n,o In our case, a phosphonium −CH 2 PPh 3 group is transformed into a −CH 2 PPh 2 −Pt−Ph unit; up to now, the activation of a phosphonium group to give a phenylphosphino derivative has been reported to occur, stoichiometrically or catalytically, only induced by Pd(0) complexes, 31e-i but in any case assisted by Pt(II) complexes.…”

Section: Resultsmentioning

confidence: 99%

C−P and C−H Bond Activations and C−C Coupling in Bis-Phosphonium Salts Induced by Platinum(II) Complexes

et al. 2003

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The reaction of [Ph 3 PCH 2 -(E)-C(Me)dC(H)PPh 3 ]Cl 2 (1b) with PtCl 2 (NCPh) 2 (1:1 molar ratio) in refluxing 2-methoxyethanol gives the ortho-metalated complex [Pt(C 6 H 3 -3-Ph-2-PPh 2 -CdC(Me)CH 2 PPh 2 -κC,C,P)Cl] (3). The synthesis of complex 3 formally involves three C-H and one C-P bond activation and one C-C bond coupling. Complex 3 reacts with excess KBr or NaI to give, after halide metathesis, the complexes [Pt(C 6 H 3 -3-Ph-2-PPh 2 -CdC(Me)CH 2 PPh 2 -κC,C,P)X] (X ) Br (4), I ( 5)). Complex 5 has been characterized by X-ray diffraction methods. The influences of several factors, such as the solvent, the platinum starting complex, and the bis-phosphonium salt, in the synthesis of 3 have been examined, and a plausible reaction mechanism for the synthesis of 3 is proposed. This mechanism is supported by the isolation of the Pt(IV) derivative [Pt(C 6 H 4 -4-F){C 6 H 3 -5-F-2-P(p-FC 6 H 4 ) 2 -CdC(Me)CH 2 P(p-FC 6 H 4 ) 2 -κC,C,P}Cl 2 ] (6), obtained by reaction of [(p-FC 6 H 4 ) 3 PCH 2 -(E)-C(Me)dC(H)P(p-FC 6 H 4 ) 3 ]Cl 2 (1f) with PtCl 2 (NCPh) 2 in refluxing 2-methoxyethanol. Complex 3 reacts with AgClO 4 and neutral monodentate (L) and bidentate (L-L) ligands, giving the cationic derivatives 12)). Complex 3 reacts with excess X 2 (Cl 2 , I 2 ) to give the expected Pt(IV) derivatives [Pt(C 6 H 3 -3-Ph-2-PPh 2 -CdC(Me)CH 2 PPh 2 -κC,C,P)-(Cl)(X) 2 ] ((X) 2 ) (Cl) 2 (13), (I) 2 ( 14)) through a typical oxidative addition process. Complex 14 has also been characterized by X-ray diffraction methods.

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Section: Resultsmentioning

confidence: 99%

C−P and C−H Bond Activations and C−C Coupling in Bis-Phosphonium Salts Induced by Platinum(II) Complexes

et al. 2003

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“…This is the case in Ru 2 (CO) 4 (SC 6 H 4 PPh 2 ) 2 , synthesized by Cabeza from dodecacarbonyltriruthenium and 2-(diphenylphosphido)thiophenol [69].…”

Section: Scheme 10mentioning

confidence: 99%

Sawhorse-type diruthenium tetracarbonyl complexes

Therrien

Süß‐Fink

2009

Coordination Chemistry Reviews

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“…An analogous ligand arrangement was observed for a similar 2-(diphenylphosphanyl)thiophenolate derivative. 16,17 Cluster 2 derives formally from the reaction of Ph 2 PN=PPh 2 C(S)NHEt, formed by HEtSNS via loss of a molecule of isothiocyanate (EtNCS), with [Ru 3 (CO) 10 (MeCN) 2 ] (Scheme 4). The fragmentation could be facilitated by the metal centre, shifting the reaction to the right side, by forming the Ru-P bond.…”

Section: Reaction Between [Ru 3 (Co) 10 (Mecn) 2 ] and Hetsnsmentioning

confidence: 99%

Reactivity of the zwitterionic ligand EtNHC(S)Ph₂PNPPh₂C(S)NEt towards [Ru₃(CO)₁₂]. Sulfur transfer and ligand fragmentation leading to the methideylamide [-N(Et)-CH(R)-] μ₃-bridging moiety

et al. 2009

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The reaction of EtNHC(S)Ph2P[double bond, length as m-dash]NP+Ph2C(S)N(-)Et (HEtSNS) with [Ru3(CO)12] has been carried out under two different experimental conditions: in the first case [Ru3(CO)12], previously turned into the labile intermediate [Ru3(CO)10(CH3CN)2], afforded, at room temperature in dichloromethane, the trinuclear clusters [Ru3(CO)11(CNEt)] (1), [Ru3(CO)9(micro-H)[(micro-S:kappa-P)Ph2PN[double bond, length as m-dash]PPh2C(S)NEt]] (2), [Ru3(CO)9(micro-H)[(micro-S:kappa-P)Ph2PN[double bond, length as m-dash]P(S)Ph2]] (3) and [Ru3(CO)10[(micro-kappa2P)Ph2PNHPPh2]] (3). Ligand fragmentation occurs via loss of EtNC or EtNCS, without sulfur transfer to the cluster core. In the second case, [Ru3(CO)12] reacted with HEtSNS in toluene at 70 degrees C, giving the trinuclear clusters , [Ru3(CO)7(CNEt)(micro3-S)[(micro2-N:eta1-C:kappa1-P)Ph2PN[double bond, length as m-dash]PPh2C(H)NEt]] (6), [Ru3(CO)8)(micro3-S)[(micro2-N:eta-C:kappa-P)Ph2PN[double bond, length as m-dash]PPh2C(H)NEt]] (6) and [Ru3(CO)6(micro3-CO)(micro3-S)(EtNC)[(micro-kappa2P) Ph2PNHPPh2]] (7). The last three compounds derive from ligand fragmentation and sulfur transfer to the metal cluster. All compounds were characterized by spectroscopy (NMR, IR) and the molecular structures of , and were determined by single-crystal X-ray diffraction. Cluster preserves the original Ru3 triangular core in which an edge is bridged by a hydride ligand and by the sulfur atom of the Ph2PN[double bond, length as m-dash]PPh2C(S)NEt ligand. Cluster shows an open triangle of Ru atoms capped by a micro3-sulfide and by the unprecedented methideylamide -N(Et)CH(R)-micro3-bridging moiety of the Ph2PN[double bond, length as m-dash]PPh2C(H)NEt ligand. It formally derives from cluster by substitution of ethyl isonitrile with one CO molecule. Finally, cluster displays a Ru3(micro3-S)(micro3-CO) trigonal bipyramidal core.

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Reactivity of 2-(Diphenylphosphanyl)thiophenol (HSC6H4PPh2) with Ruthenium and Osmium Carbonyl Complexes; Breaking of HSC6H4PPh2 into Sulfide, Phenyl and Diphenylphosphanyl Ligands on a Triruthenium Cluster

Cited by 20 publications

References 44 publications

C−P and C−H Bond Activations and C−C Coupling in Bis-Phosphonium Salts Induced by Platinum(II) Complexes

C−P and C−H Bond Activations and C−C Coupling in Bis-Phosphonium Salts Induced by Platinum(II) Complexes

Sawhorse-type diruthenium tetracarbonyl complexes

Reactivity of the zwitterionic ligand EtNHC(S)Ph₂PNPPh₂C(S)NEt towards [Ru₃(CO)₁₂]. Sulfur transfer and ligand fragmentation leading to the methideylamide [-N(Et)-CH(R)-] μ₃-bridging moiety

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Reactivity of 2-(Diphenylphosphanyl)thiophenol (HSC6H4PPh2) with Ruthenium and Osmium Carbonyl Complexes; Breaking of HSC6H4PPh2 into Sulfide, Phenyl and Diphenylphosphanyl Ligands on a Triruthenium Cluster

Cited by 20 publications

References 44 publications

C−P and C−H Bond Activations and C−C Coupling in Bis-Phosphonium Salts Induced by Platinum(II) Complexes

C−P and C−H Bond Activations and C−C Coupling in Bis-Phosphonium Salts Induced by Platinum(II) Complexes

Sawhorse-type diruthenium tetracarbonyl complexes

Reactivity of the zwitterionic ligand EtNHC(S)Ph2PNPPh2C(S)NEt towards [Ru3(CO)12]. Sulfur transfer and ligand fragmentation leading to the methideylamide [-N(Et)-CH(R)-] μ3-bridging moiety

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Reactivity of the zwitterionic ligand EtNHC(S)Ph₂PNPPh₂C(S)NEt towards [Ru₃(CO)₁₂]. Sulfur transfer and ligand fragmentation leading to the methideylamide [-N(Et)-CH(R)-] μ₃-bridging moiety